Process for converting intermediates in a process for producing trans-1,2-difluoroethylene (hfo-1132e)

Abstract

In the first step reaction for producing 1,1,2-trifluoroethane (HFC-143) from 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) as part of the overall process for producing trans-1,2-difluoroethylene (HFO-1132E), several intermediates and / or byproducts are formed, some of which can be considered desirable and others of which can be considered undesirable. The overall reaction process and / or specific reaction conditions for producing 1,1,2-trifluoroethane (HFC-143) from 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) can be selectively adjusted to effectively convert the desired intermediates to the desired product 1,1,2-trifluoroethane (HFC-143) and / or minimize the formation of undesirable byproducts.

Description

[0001] Cross-references to related applications

[0002] This application claims priority to U.S. Patent Application No. 18 / 988,359, filed December 19, 2024, entitled “METHODS FOR CONVERTING INTERMEDIATES IN PROCESSES FOR PRODUCING trans-1,2-DIFLUOROETHYLENE (HFO-1132E)”, which is pursuant to 35 USC. 119(e) refers to U.S. Provisional Application No. 63 / 613,982, filed December 22, 2023, entitled “METHODS FOR CONVERTING INTERMEDIATES IN PROCESSES FOR PRODUCING trans-1,2-DIFLUOROETHYLENE (HFO-1132E)”; Provisional Application No. 63 / 718,445, filed November 08, 2024, entitled “METHODS FOR CONVERTING INTERMEDIATES IN PROCESSES FOR PRODUCING trans-1,2-DIFLUOROETHYLENE (HFO-1132E)”; and Provisional Application No. 63 / 718,445, filed November 25, 2024, entitled “METHODS FOR CONVERTING INTERMEDIATES IN PROCESSES FOR PRODUCING trans-1,2-DIFLUOROETHYLENE”. The rights of provisional application No. 63 / 724,856 (HFO-1132E) are hereby granted, the entire disclosure of which is incorporated herein by reference in its entirety. Technical Field

[0003] This disclosure relates in its entirety to a method for producing trans-1,2-difluoroethylene (HFO-1132E) from 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113), and more specifically to a method for managing the formation and / or conversion of intermediates that may be formed in the HFO-1132E process. Background Technology

[0004] Recent discoveries have revealed an increasing versatility for 1,2-difluoroethylene (HFO-1132) in various applications. HFO-1132 can exist as a mixture of two geometric isomers, namely the E or trans isomer and the Z or cis isomer, which can be used alone or in various proportions. Potential end-use applications of HFO-1132 include refrigerants, used alone or in blends with other components, as a solvent for organic materials, and as a chemical intermediate for the synthesis of other halogenated hydrocarbon solvents.

[0005] Certain intermediates and / or byproducts are generated during the production of HFO-1132. It is desirable to convert any useful intermediates into the desired product and / or minimize the formation of any undesirable byproducts during the production of the desired product HFO-1132. Summary of the Invention

[0006] HFO-1132, and particularly HFO-1132E, is produced from 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113). In a first step, 1,1,2-trifluoroethane (HFC-143) is produced by hydrogenating CFC-113 with hydrogen in the presence of a catalyst to produce HFC-143. Then, in the presence of a catalyst, HFC-143 is dehydrofluorinated to produce trans-1,2-difluoroethylene (HFO-1132E) and / or cis-1,2-difluoroethylene (HFO-1132Z). HFO-1132Z can then optionally be isomerized to produce HFO-1132E.

[0007] It has been found that in the first step of producing HFC-143 from CFC-113, several intermediates and / or byproducts are formed, some of which are considered desirable intermediates and others are considered undesirable byproducts. This disclosure is based on the finding that the overall reaction method and / or specific reaction conditions for the first step of producing HFC-143 from CFC-113 can be selectively adjusted to advantageously convert the desired intermediates into the desired product HFC-143 and / or minimize the formation of undesirable byproducts.

[0008] In one form, this disclosure provides a method for producing HFC-143, the method comprising: reacting at least one of CFC-113, 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 1-chloro-1,2,2-trifluoroethane (HCFC-133), and 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a) in the presence of a catalyst at a temperature above 150°C to produce HFC-143.

[0009] In another form, this disclosure provides a method for producing HFC-143, the method comprising: hydrogenating CFC-113 by reacting it with hydrogen to produce a first product composition comprising at least one of HCFC-133b, HCFC-133 and HCFC-123a and HFC-143; and hydrogenating at least one of HCFC-133b, HCFC-133 and HCFC-123a from the first product composition at a temperature above 150°C in the presence of a catalyst to produce a second product composition comprising HFC-143. Attached Figure Description

[0010] Figure 1 This is a schematic diagram of a single reactor layout for converting 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) to 1,1,2-trifluoroethane (HFC-143).

[0011] Figure 2 This is a schematic diagram of a dual-reactor layout used to convert CFC-113 to HFC-143. Detailed Implementation

[0012] I. Definition

[0013] As used herein, the singular forms “an” and “the” include the plural, unless the context clearly specifies otherwise. Furthermore, when a quantity, concentration, or other value or parameter is given as a range, preferred range, or a list of preferred upper and lower limits, this should be understood as specifically disclosing all ranges formed by any pair of any upper or preferred value with any lower or preferred value, regardless of whether the range is disclosed individually. Where numerical ranges are described herein, unless otherwise stated, the range is intended to include its endpoints, as well as all integers and fractions within that range. When a range is defined, the scope of this disclosure is not intended to be limited to the specific values ​​described.

[0014] As used herein, the phrase “any range encompassing any two of these values ​​as endpoints” or “any range using any two of the aforementioned values ​​as endpoints” literally means that any range can be selected from any two values ​​listed preceding such a phrase, regardless of whether those values ​​are in the lower or higher parts of the list. For example, a pair of values ​​can be selected from two lower values, two higher values, or a lower and a higher value. For example, a range following the phrase as low as 1, 2, or 3, or as high as 8, 9, or 10, encompasses ranges including 1 to 10, or 2 to 8, or 3 to 9.

[0015] In the following examples, the name “R” may be used in conjunction with various fluorinated molecules described herein, such as “R-143” which refers to 1,1,2-trifluoroethane (HFC-143).

[0016] As used in this article, the phrase “desired product” is 1,1,2-trifluoroethane (HFC-143).

[0017] As used herein, the phrase “desired intermediate” includes one or more of 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 1-chloro-1,2,2-trifluoroethane (HCFC-133), and 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a).

[0018] As used herein, the phrase “undesirable byproducts” includes one or more of the following: 1,1,1-trifluoroethane (HFC-143a), ethane (HC-170), chloroethane (HCC-160), 1,1-difluoroethane (HFC-152a), and HCFC-142 isomers (e.g., 1-chloro-1,2-difluoroethane (HCFC-142a), 1-chloro-2,2-difluoroethane (HCFC-142), and / or 1-chloro-1,1-difluoroethane (HCFC-142b)).

[0019] As used herein, the phrase “total moles of organic components based on composition” refers only to carbon-containing components and excludes or covers non-carbon-containing components such as hydrogen (H2) or hydrogen chloride (HCl).

[0020] As used in this article, the conversion rate of reactant molecules (molecule X) during the reaction is calculated using the following equation:

[0021] Conversion rate of molecule X % = (100 - molar amount of molecule X in the organic component of the product mixture)

[0022] As used in this paper, the selectivity for the molecules (molecule X) formed during the reaction is calculated using the following equation:

[0023] Selectivity for molecule X % = molar percentage of molecule X in the organic component of the product mixture / (100 - molar percentage of reactant molecules in the organic component of the product mixture) × 100.

[0024] As used herein, the increase in the amount of such molecules formed in the second product mixture after the second reaction step, compared to the amount of molecules (molecule X) in the first product mixture formed in the first reaction step, is calculated using the following equation:

[0025] The increase in molecule X by % = ((molar percentage of molecule X in the organic component of the second product mixture - molar percentage of molecule X in the organic component of the first product mixture) / (molar percentage of molecule X in the organic component of the first product mixture) × 100.

[0026] II. Overview

[0027] This disclosure provides a method for producing E-1,2-difluoroethylene (HFO-1132E) from 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) according to a three-step process (“Process 1”) shown below, the three-step process comprising the following three steps: (i) hydrogenating CFC-113 to produce 1,1,2-trifluoroethane (HFC-143); (ii) dehydrofluorinating HFC-143 to produce a mixture of trans-1,2-difluoroethylene (HFO-1132E) and cis-1,2-difluoroethylene (HFO-1132Z); and (iii) optionally isomerizing HFO-1132Z to HFO-1132E.

[0028] The schematic equations for the three steps of process 1 are shown below:

[0029] Process 1

[0030] (i) CFCl2-CF2Cl (CFC-113) + H2 CFH2-CF2H(HFC-143)+ HCl

[0031] (ii) CFH2-CF2H trans-CFH = CHF(HFO - 1132E) + cis-CFH = CFH(HFO - 1132Z) + HF

[0032] (iii) Cis -CFH = CFH (HFO - 1132Z) The trans form -CFH = CHF(HFO - 132E)

[0033] Step (i) can be carried out via an intermediate of 1,1,2-trifluoroethylene (HFO-1123), wherein CFC-113 is first hydrogenated to produce HFO-1123 as an intermediate, which is then hydrogenated to produce HFC-143.

[0034] Furthermore, as discussed herein, it has been found that in step (i), several intermediates and / or byproducts are formed, some of which may be considered as desired intermediates and others as undesirable byproducts. It has also been found that the overall reaction method and / or specific reaction conditions of step (i) can be selectively adjusted to advantageously convert desired intermediates into the desired product HFC-143 and / or minimize the formation of undesirable byproducts.

[0035] Further details regarding each of steps (i), (ii), and (iii) are shown below.

[0036] III. Step (i)

[0037] General process

[0038] The hydrogenation reaction in step (i) can be carried out in a gaseous or vapor phase in a suitable reactor (e.g., a tubular reactor made of a temperature- and / or corrosion-resistant material, such as nickel and its alloys, including Hastelloy (e.g., Hastelloy C276), Inconel (e.g., Inconel 600), Incoloy, and Monel), and the vessel can be lined with a fluoropolymer.

[0039] The reactor used for the hydrogenation reaction in step (i) may first be cleaned and flushed with an inert gas such as nitrogen, and then filled with a catalyst (such as those described below). The catalyst may be pretreated in the reactor, such as by drying as further described below, before the reactants are metered into the reactor to initiate the reaction.

[0040] The hydrogenation process in step (i) can proceed through a catalyst bed in a downward or upward direction. The product feed can be passed through one or more scrubbers to remove unwanted byproducts, such as hydrogen fluoride (HF) and / or hydrogen chloride (HCl), and the reaction products can be collected, for example, by capture in a cooled cylinder.

[0041] As discussed in further detail below, the catalyst and process conditions play an important role in the hydrogenation reaction in step (i).

[0042] catalyst

[0043] In the hydrogenation reaction of step (i), the catalyst may comprise a metal, such as palladium, platinum, rhodium, ruthenium, iron, cobalt, or nickel. Specifically, the catalyst active for the catalytic reaction may preferably be palladium (Pd), platinum (Pt), or a combination of palladium and platinum.

[0044] catalyst support

[0045] In the hydrogenation reaction of step (i), the catalyst can be supported on a suitable support, such as carbon or alumina (alumina – Al₂O₃). The carbon can be activated carbon. The alumina can be alpha (α) alumina, theta (θ) alumina, delta (δ) alumina, or gamma (γ) alumina. A supported catalyst can be produced by impregnating any suitable support with a solution of a compound of the desired metal component. The support can also be in pellet form. After the impregnation step, the solvent can be removed by heating or under vacuum to obtain a solid material, which can be further dried, calcined, and reduced to form an active metal catalyst.

[0046] In the hydrogenation reaction of step (i), the catalyst may be palladium on a carbon support, platinum on a carbon support, rhodium on a carbon support, and / or palladium, platinum, or rhodium on an alumina support. The catalyst may be palladium on a carbon support. The catalyst may be palladium on an α-alumina support.

[0047] The metal catalysts supported on various catalyst supports used in the hydrogenation reaction of step (i) are listed in Table 1 below.

[0048] Table 1: Supported metal catalysts – step (i) hydrogenation reaction

[0049]

[0050] catalyst loading

[0051] For each catalyst / support combination (per row) in Table 1 used in the hydrogenation reaction of step (i), the amount of metal supported on the support is less than to about 0.01 wt%, about 0.05 wt%, about 0.1 wt%, about 0.2 wt%, about 0.3 wt%, about 0.4 wt%, about 0.5 wt%, about 1 wt%, or more than about 2 wt%, about 3 wt%, about 5 wt%, about 10 wt%, about 20 wt%, about 30 wt%, about 40 wt%, about 50 wt%, or in any range covered by two of the foregoing values ​​as endpoints, for example, based on the total weight of the catalyst and support, about 0.01 wt% to about 20 wt%, about 0.01 wt% to about 10 wt%, about 0.1 wt% to about 10 wt%, 0.2 wt% to about 10 wt%, about 0.5 wt% to about 5 wt%, about 1 wt% to about 5 wt%, about 1 wt% to about 4 wt%, or about 2 wt% to about 4 wt%. For supported noble metal catalysts (such as Pd or Pt) or Rh Based on the total weight of the catalyst and support, the metal loading can be from about 0.01% by weight to about 5% by weight. Specific examples of other suitable ranges are shown in Table 2 below.

[0052] Table 2 – Catalysts (Pd, Pt, Rh) on supports (activated carbon, alpha (α)-Al2O3, sita (θ)-Al2O3, delta) Loading amount on (δ)-Al2O3 or gamma (γ)-Al2O3 – for each catalyst / support combination in Table 1 (per row) – step (i) hydrogenation reaction

[0053]

[0054] BET surface area

[0055] BET (Brunauer, Emmett, and Teller) analysis is a standard method for determining surface area from nitrogen adsorption isotherms. The BET surface area of ​​a catalyst can be measured using a TriStar II Micromeritics instrument. Prior to BET analysis, the catalyst sample is degassed using a FlowPrep 060 instrument.

[0056] For each catalyst / support combination (per row) in Table 1 used in the hydrogenation reaction of step (i), the BET surface area can be as low as approximately 0.5 m². 2 / g, approximately 1m 2 / g, approximately 3m 2 / g, approximately 5m 2 / g, approximately 10m 2 / g, approximately 15m 2 / g, approximately 20m 2 / g 2 Approximately 30m 2 / g, approximately 40m 2 / g, approximately 50m 2 / g, approximately 100m 2 / g, approximately 200m 2 / g or up to about 250m 2 / g, approximately 300m 2 / g, approximately 400m 2 / g, approximately 500m 2 / g, approximately 600m 2 / g, approximately 700m 2 / gm 2 Approximately 800m 2 / g, approximately 900m 2 / g, approximately 1000m 2 / g, approximately 2000m 2 / g, approximately 3000m 2 / g, or within any range covered by any of the aforementioned values ​​as endpoints, for example, about 0.5m. 2 / g to approximately 3000m 2 / g, approximately 1m 2 / g to approximately 2000m 2 / g, approximately 1000m 2 / g to approximately 2000m2 / g, approximately 0.5m 2 / g to approximately 500m 2 / g, approximately 0.5m 2 / g to approximately 300m 2 / g, approximately 0.5m 2 / g to approximately 5m 2 / g or approximately 200mg 2 / g to approximately 300m 2 / g.

[0057] For the carbon-supported metal catalyst (Pd, Pt, Rh) used in the hydrogenation reaction in step (i), the BET surface area can be approximately 100 m². 2 / g to approximately 3000m 2 / g, preferably about 200m 2 / g to approximately 2000m 2 / g, more preferably about 500m 2 / g to approximately 1500m 2 / g, and the optimal value is approximately 1000m 2 / g to approximately 1500m 2 / g. Specific examples of other suitable ranges are shown in Table 3a below.

[0058] For the alumina-supported metal catalyst (Pd, Pt, Rh) used in the hydrogenation reaction of step (i), which is alpha (α)-Al₂O₃, theta (θ)-Al₂O₃, delta (δ)-Al₂O₃, or gamma (γ)-Al₂O₃, the BET surface area can be approximately 0.5 m². 2 / g to approximately 500m 2 / g, preferably about 1m 2 / g to approximately 200m 2 / g, more preferably about 1m 2 / g to approximately 100m 2 / g, and the optimal value is approximately 1m 2 / g to approximately 20m 2 / g. Specific examples of other suitable ranges are shown in Table 3b below.

[0059] Table 3a – BET surface area of ​​catalysts (Pd, Pt, Rh) on support (activated carbon) – step (i) hydrogenation reaction

[0060]

[0061] Table 3b – Catalysts (Pd, Pt, Rh) on supports (alpha (α)-Al₂O₃, sita (θ)-Al₂O₃, delta (δ)-Al₂O₃) BET surface area on Al2O3 or gamma (γ)-Al2O3 – step (i) hydrogenation reaction

[0062]

[0063] Catalyst pretreatment

[0064] For each catalyst / support combination (per row) in Table 1 used in the hydrogenation reaction of step (i), the catalyst can be pretreated in various ways to improve its performance and efficiency in the reaction. For example, the catalyst can be dried at elevated temperatures, as low as about 200°C, about 250°C, about 300°C, about 350°C, about 360°C, about 370°C, or as high as about 380°C, about 390°C, about 400°C, about 450°C, about 500°C, about 600°C, about 700°C, or in any range covered by two of the foregoing values ​​as endpoints, such as about 200°C to about 400°C, about 200°C to about 350°C, about 250°C to about 350°C, about 250°C to about 300°C, or about 260°C to about 300°C. Specific examples of other suitable ranges are shown in Table 4 below.

[0065] Table 4 – Catalysts (Pd, Pt, Rh) on supports (activated carbon, alpha (α)-Al2O3, sita (θ)-Al2O3, delta Pretreatment drying temperature on (δ)-Al2O3 or gamma (γ)-Al2O3 – for each catalyst / support combination in Table 1 (per row) – Step (i) Hydrogenation reaction

[0066]

[0067] For each catalyst / support combination (per row) in Table 1 used in the hydrogenation reaction of step (i), the catalyst (Pd, Pt, Rh) may be exposed to an inert gas, such as N2, as part of the catalyst pretreatment. The pretreatment process may take as little as about 1 hour, about 2 hours, about 3 hours, about 4 hours, or as long as about 5 hours, about 6 hours, about 10 hours, about 20 hours, or any range covered by two of the foregoing values ​​as endpoints, such as about 2 hours to about 4 hours, for example about 1 hour to about 20 hours, about 2 hours to about 10 hours, about 3 hours to about 6 hours, or about 4 hours to about 5 hours.

[0068] Reaction conditions – temperature

[0069] For the reaction using each catalyst / support combination (per row) in Table 1, the reaction temperature of the hydrogenation reaction in step (i) can be as low as about 100°C, about 125°C, about 150°C, about 200°C, about 250°C, or as high as about 300°C, about 350°C, about 400°C, or any range covered by two of the foregoing values ​​as endpoints, such as, for example, about 100°C to about 400°C, or about 125°C to about 350°C, about 150°C to about 300°C, or about 200°C to about 250°C. The temperature can preferably be about 100°C to about 350°C, and more preferably about 200°C to about 300°C. Specific examples of other suitable ranges are shown in Table 5 below.

[0070] Table 5 – When using a carrier (activated carbon, alpha (α)-Al2O3, sita (θ)-Al2O3, delta (δ)-Al2O3 or gamma-hydroxyl powder) Reaction temperatures on catalysts (Pd, Pt, Rh) on (γ-Al2O3) – Table 1 shows the reaction temperatures for each catalyst / support combination (per (Line) – Step (i) Hydrogenation reaction

[0071]

[0072] As demonstrated in the examples herein, the selectivity of the hydrogenation reaction in step (i) for the desired product 1,1,2-trifluoroethane (HFC-143) can increase with temperature. However, the overall selectivity for 1,1,2-trifluoroethane (HFC-143) and its associated recyclable intermediates such as 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 1-chloro-1,2,2-trifluoroethane (HCFC-133), 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a), and trifluoroethylene (HFO-1123) can decrease with higher temperatures, due to the presence of ethane (HC-17). Increased formation of undesirable byproducts such as 0), chloroethane (HCC-160), HCFC-142 isomers (e.g., 1-chloro-1,2-difluoroethane (HCFC-142a), 1-chloro-2,2-difluoroethane (HCFC-142) and / or 1-chloro-1,1-difluoroethane (HCFC-142b)), 1,1-difluoroethane (HFC-152a), and 1,1,1-trifluoroethane (HFC-143a).

[0073] Reaction conditions – contact time

[0074] For each catalyst / support combination (per row) in Table 1, the contact time between the reactants and the catalyst (Pd, Pt, Rh) in the hydrogenation reaction of step (i) can be as short as about 0.1 seconds, about 1 second, about 2 seconds, about 5 seconds, about 10 seconds, about 15 seconds, or about 20 seconds, or as long as about 25 seconds, about 30 seconds, about 40 seconds, about 50 seconds, about 60 seconds, about 80 seconds, or about 120 seconds, or any range covered by two of the foregoing values ​​as endpoints, such as about 0.1 seconds to about 120 seconds, about 1 second to about 60 seconds, about 5 seconds to about 50 seconds, about 10 seconds to about 40 seconds, about 15 seconds to about 30 seconds, or about 20 seconds to about 25 seconds. For example, the contact time can be from about 1 second to about 60 seconds. Specific examples of other suitable ranges are shown in Table 6 below.

[0075] Table 6 – Reactants and Supports (Activated Carbon, Alpha (α)-Al₂O₃, Theta (θ)-Al₂O₃, Delta (δ)-Al₂O₃ or Contact time of catalysts (Pd, Pt, Rh) on gamma (γ)-Al2O3 – Table 1 for each catalyst / support combination (per (Line) – Step (i) Hydrogenation reaction

[0076]

[0077] Reaction conditions – pressure

[0078] For each catalyst / support combination (per row) in Table 1, the reactor internal pressure during the hydrogenation reaction in step (i) can be as low as about 1 psig, about 3 psig, about 5 psig, about 10 psig, about 15 psig, about 20 psig, about 30 psig, about 35 psig, or about 40 psig, or as high as about 90 psig, about 100 psig, about 120 psig, about 150 psig, about 200 psig, or about 250 psig, or about 300 psig, or in any range covered by two of the foregoing values ​​as endpoints, such as about 1 psig to about 300 psig, about 3 psig to about 250 psig, about 5 psig to about 200 psig, about 10 psig to about 150 psig, about 15 psig to about 120 psig, about 20 psig to about 100 psig, about 30 psig to about 90 psig, or about 35 psig to about 40 psig. For example, the pressure can be from about 10 psig to about 200 psig. Specific examples of other suitable ranges are shown in Table 7 below.

[0079] Table 7 – Supports used (activated carbon, alpha (α)-Al2O3, theta (θ)-Al2O3, delta (δ)-Al2O3 or gamma) Reaction pressure of catalysts (Pd, Pt, Rh) on (γ)-Al2O3 – for each catalyst / support combination in Table 1 (per row) – step Step (i) hydrogenation reaction

[0080]

[0081] Reaction conditions – hydrogen molar ratio

[0082] For each catalyst / support combination (per row) in Table 1 used in the hydrogenation reaction of step (i), the molar ratio of hydrogen to CFC-113 can be as low as about 2:1, about 3:1, about 4:1, about 5:1, about 5.5:1, or as high as about 6:1, about 6.5:1, about 7.5:1, or about 8:1, about 12:1, about 15:1, or about 20:1, for example, or within any range covered by two of the foregoing values ​​as endpoints. The molar ratio of hydrogen to CFC-113 can preferably be from about 3:1 to about 15:1, and more preferably from about 4:1 to about 10:1.

[0083] Product – Selectivity for HFC-143

[0084] As demonstrated in the examples herein, for each catalyst / support combination (per row) in Table 1, the hydrogenation step (i) can achieve selectivity for the desired product 1,1,2-trifluoroethane (HFC-143) based on the total molar number of organic components in the composition, which is at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, and for each of the foregoing, less than or equal to 100%, or within any range covered by two of the foregoing values ​​as endpoints, such as about 20% to about 90%, about 30% to about 80%, about 40% to about 80%, or about 50% to about 80%. Specific examples of other suitable ranges are shown in Table 8 below.

[0085] Table 8 – Supports used (activated carbon, alpha (α)-Al2O3, theta (θ)-Al2O3, delta (δ)-Al2O3 or gamma) Selectivity of catalysts (Pd, Pt, Rh) on (γ)-Al2O3 for the desired product HFC-143 – Table 1 for each catalyst / Support combination (per row) – Step (i) hydrogenation reaction

[0086]

[0087] Methods for transforming intermediates

[0088] As discussed below, during the hydrogenation reaction in step (i), several intermediates and / or byproducts may be formed, some of which may be considered as desired intermediates and others as undesirable byproducts. The overall reaction method and / or specific reaction conditions of step (i) may be selectively adjusted to effectively convert the desired intermediates into the product 1,1,2-trifluoroethane (HFC-143) and / or minimize the formation of undesirable byproducts.

[0089] Specifically, using each catalyst / support combination (per row) in Table 1, the hydrogenation reaction for step (i) to produce 1,1,2-trifluoroethane (HFC-143) from 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) can yield several desired intermediates, such as 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 1-chloro-1,2,2-trifluoroethane (HCFC-133), and / or 1,2-dichloro-1,1,2-trifluoroethane (HCFC-143). C-123a), and several undesirable byproducts such as 1,1,1-trifluoroethane (HFC-143a), ethane (HC-170), chloroethane (HCC-160), 1,1-difluoroethane (HFC-152a) and / or HCFC-142 isomers (e.g., 1-chloro-1,2-difluoroethane (HCFC-142a), 1-chloro-2,2-difluoroethane (HCFC-142) and / or 1-chloro-1,1-difluoroethane (HCFC-142b)).

[0090] It has been found that the hydrogenation reaction in step (i) using each catalyst / support combination (each row) in Table 1 forms intermediates 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 1-chloro-1,2,2-trifluoroethane (HCFC-133), and / or 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a), and each of 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 1-chloro-1,2,2-trifluoroethane (HCFC-133), and / or 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a) is less reactive than 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) used to produce 1,1,2-trifluoroethane (HFC-143).

[0091] However, despite the foregoing, it has also been found that each of 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 1-chloro-1,2,2-trifluoroethane (HCFC-133), and / or 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a) can be converted to 1,1,2-trifluoroethane (HFC-143) via the methods and reaction conditions described herein, and in light of this finding, 1-chloro-1,1,2- Trifluoroethane (HCFC-133b), 1-chloro-1,2,2-trifluoroethane (HCFC-133) and / or 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a) can be considered “desirable intermediates” because each of the above can be converted into the desired product 1,1,2-trifluoroethane (HFC-143) in order to increase the overall efficiency of step (i) process using each catalyst / support combination (per row) in Table 1.

[0092] For example, when the desired intermediates are formed in the hydrogenation reaction of step (i) using each catalyst / support combination (per row) in Table 1, these intermediates can potentially be recycled as reactants for the hydrogenation reaction and can be further reacted to form 1,1,2-trifluoroethane (HFC-143). However, recycling these intermediates can be difficult because such intermediates are less reactive than 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) and may therefore accumulate or pile up elsewhere in the reactor and / or overall process architecture, thereby hindering the selectivity, yield, and purity of the desired product 1,1,2-trifluoroethane (HFC-143). The reaction conditions and layouts disclosed herein are designed to facilitate the recycling and further reaction of the aforementioned intermediates to result in the formation of the desired 1,1,2-trifluoroethane (HFC-143).

[0093] This disclosure provides single-reactor and two-reactor methods to facilitate the conversion of intermediates into the desired product 1,1,2-trifluoroethane (HFC-143).

[0094] i. Single reactor method

[0095] In the single-reactor method, the following will combine Figure 1 The overall reaction method is described in more detail, although, in conjunction with certain aspects described below, reaction conditions can be selectively adjusted to maximize the production of desired products and intermediates and minimize the production of undesirable byproducts, wherein the reactor in the single-reactor method can be used in conjunction with a reaction carried out at a higher temperature and using a more reactive catalyst compared to the conditions described above.

[0096] As demonstrated in the examples herein, increasing the reaction temperature and / or using a more reactive catalyst facilitates the conversion of less reactive but desirable intermediates, including 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 1-chloro-1,2,2-trifluoroethane (HCFC-133), and 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a), into the desired product 1,1,2-trifluoroethane (HFC-143).

[0097] refer to Figure 1 A feed stream 100 containing CFC-113 and a feed stream 102 containing hydrogen (H2) enter reactor 106. Inside reactor 106, CFC-113 undergoes a hydrogenation reaction in step (i) to produce HFC-143.

[0098] a. Single reactor method – reactor temperature

[0099] In the single-reactor method, the reaction temperature within reactor 106 can be as low as about 200°C, about 205°C, about 210°C, about 215°C, about 220°C, about 225°C, about 230°C, about 235°C, about 240°C, about 245°C, about 250°C, about 255°C, or as high as about 260°C, about 265°C, about 270°C, about 275°C, about 280°C, about 285°C, about 290°C, about 295°C, about 300°C, about 305°C, about 310°C, about 315°C, about 320°C, about 325°C, about 350°C, or within any range covered by any two of the foregoing values ​​as endpoints. For example, the reaction temperature can be about 200°C to about 350°C, about 200°C to about 325°C, about 210°C to about 325°C, about 220°C to about 325°C, about 230°C to about 325°C, about 240°C to about 325°C, about 250°C to about 325°C, about 260°C to about 325°C, about 270°C to about 325°C, or about 280°C to about 320°C. Specific examples of other suitable ranges are shown in Table 9 below.

[0100] Table 9 – Supports used (activated carbon, alpha (α)-Al₂O₃, theta (θ)-Al₂O₃, delta (δ)-Al₂O₃ or gamma) Reactor temperature ranges for single-reactor methods using catalysts (Pd, Pt, or Rh) on (γ)-Al₂O₃ – Table 1 for each catalyst Agent / carrier combination (per row) – Step (i) hydrogenation reaction

[0101]

[0102] b. Single reactor method – reaction conditions

[0103] Each catalyst / support combination (per row) in Table 1 can be used in a reactor of a single-reactor method for carrying out the hydrogenation reaction in step (i). The catalyst / support combination used in the reactor of the single-reactor method can preferably be palladium metal on an α-alumina support, or more preferably palladium metal on a carbon support (Pd / C). The catalyst loading can be relatively high to facilitate the conversion of less reactive intermediates. For example, based on the combined weight of palladium metal and the carbon or α-alumina support, the Pd loading on the carbon or α-alumina support can be from about 0.1 wt% to about 10 wt% of palladium metal, such as about 0.1 wt%, about 0.2 wt%, about 0.5 wt%, about 2 wt%, about 3 wt%, 4 wt%, about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, or about 10 wt% of palladium metal, or within any range covered by any two of the foregoing values ​​as endpoints. A summary of the preferred catalysts and supports, loadings, and temperatures discussed above is presented in Table 10 below.

[0104] Table 10 – Total Preferred Catalysts (Palladium, Platinum, Rhodium) on Supports (Carbon, α-Alumina) for Single-Reactor Processes Conclusion – Step (i) Hydrogenation reaction

[0105]

[0106]

[0107] Each catalyst / support combination (per row) in Table 1 used in the reactor of the single-reactor method for carrying out the hydrogenation reaction in step (i) can be pretreated or activated by a variety of methods to improve its performance and efficiency in the reaction. For example, the catalyst can be dried at elevated temperatures, as low as about 200°C, about 250°C, about 300°C, about 350°C, about 360°C, about 370°C or as high as about 380°C, about 390°C, about 400°C, about 450°C, about 500°C, about 600°C, about 700°C, or in any range covered by two of the foregoing values ​​as endpoints, such as about 200°C to about 700°C, about 250°C to about 600°C, about 300°C to about 500°C, about 350°C to about 450°C, about 360°C to about 390°C, or about 370°C to about 380°C. The catalyst can be dried at a temperature of about 200°C to about 700°C, preferably about 200°C to about 500°C, and most preferably about 200°C to about 300°C.

[0108] As part of catalyst pretreatment, each catalyst / support combination (per row) in Table 1 used in the reactor of the single-reactor method for carrying out the hydrogenation reaction in step (i) may be exposed to an inert gas, such as N2. The pretreatment process may take as little as about 1 hour, about 2 hours, about 3 hours, or as long as about 4 hours, about 5 hours, about 6 hours, about 10 hours, about 20 hours, or any range covered by two of the foregoing values ​​as endpoints, such as about 1 hour to about 20 hours, about 2 hours to about 10 hours, about 3 hours to about 6 hours, or about 4 hours to about 5 hours. The catalyst may be exposed to an inert gas (such as N2) for about 1 hour to about 20 hours, preferably about 1 hour to about 10 hours, and most preferably about 1 hour to about 3 hours.

[0109] In one example, the hydrogenation reaction in step (i) can be carried out in reactor 106 of a single-reactor method using a palladium metal catalyst (Pd / C) on a catalyst support at a temperature of about 200°C to about 350°C, wherein the Pd loading is about 1% to about 5% by weight of palladium metal based on the combined weight of palladium metal and carbon support.

[0110] In another example, the hydrogenation reaction in step (i) can be carried out in reactor 106 of a single-reactor method using a palladium metal catalyst (Pd) on a catalyst support (activated carbon) at a temperature of about 200°C to about 325°C, wherein the Pd loading is about 2% to about 4% by weight of palladium metal based on the combined weight of palladium metal and carbon support.

[0111] In another example, the hydrogenation reaction in step (i) can be carried out in reactor 106 of a single-reactor method using a palladium metal catalyst (Pd / C) on a catalyst support at a temperature of about 250°C to about 350°C, wherein the Pd loading is about 4% by weight of palladium metal based on the combined weight of palladium metal and carbon support.

[0112] In one example, the hydrogenation reaction in step (i) can be carried out in reactor 106 of a single-reactor method using a platinum metal catalyst (Pt / C) on a catalyst support at a temperature of about 200°C to about 350°C, wherein the Pt loading is about 1% to about 5% by weight of platinum metal based on the combined weight of platinum metal and carbon support.

[0113] In another example, the hydrogenation reaction in step (i) can be carried out in reactor 106 of a single-reactor method using a platinum metal catalyst (Pt) on a catalyst support (activated carbon) at a temperature of about 200°C to about 325°C, wherein the Pt loading is about 2% to about 4% by weight of platinum metal based on the combined weight of platinum metal and carbon support.

[0114] In another example, the hydrogenation reaction in step (i) can be carried out in reactor 106 of a single-reactor method using a platinum metal catalyst (Pt / C) on a catalyst support at a temperature of about 250°C to about 350°C, wherein the Pt loading is about 4% by weight of platinum metal based on the combined weight of platinum metal and carbon support.

[0115] In one example, the hydrogenation reaction in step (i) can be carried out in reactor 106 of a single-reactor method using a rhodium metal catalyst (Rh / C) on a catalyst support at a temperature of about 200°C to about 350°C, wherein the Rh loading is about 1% to about 5% by weight of rhodium metal based on the combined weight of the rhodium metal and the carbon support.

[0116] In another example, the hydrogenation reaction in step (i) can be carried out in reactor 106 of a single-reactor method using a rhodium metal catalyst (Rh) on a catalyst support (activated carbon) at a temperature of about 200°C to about 325°C, wherein the Rh loading is about 2% to about 4% by weight of rhodium metal based on the combined weight of rhodium metal and carbon support.

[0117] In another example, the hydrogenation reaction in step (i) can be carried out in reactor 106 of a single-reactor method using a rhodium metal catalyst (Rh / C) on a catalyst support at a temperature of about 250°C to about 350°C, wherein the Rh loading is about 4% by weight of rhodium metal based on the combined weight of the rhodium metal and the carbon support.

[0118] c. Single-reactor method – product stream from the reactor

[0119] Refer again Figure 1 In the single-reactor method, the hydrogenation reaction in step (i) within reactor 106 produces a product stream 108 (before any post-processing steps), which contains the target product 1,1,2-trifluoroethane (HFC-143), recyclable intermediates such as 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 1-chloro-1,2,2-trifluoroethane (HCFC-133), and / or 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a), unreacted starting materials such as hydrogen (H2) and 1,1,2-trichloro-1,2,2-trifluoroethane. - Trifluoroethane (CFC-113), and other undesirable byproducts such as ethane (HC-170), 1,1-difluoroethane (HFC-152a), HCFC-142 isomers (e.g., 1-chloro-1,2-difluoroethane (HCFC-142a), 1-chloro-2,2-difluoroethane (HCFC-142) and / or 1-chloro-1,1-difluoroethane (HCFC-142b)), chloroethane (HCC-160), 1,1,1-trifluoroethane (HFC-143a), hydrogen chloride (HCl), and hydrogen fluoride (HF).

[0120] As discussed below, the product stream 108 from reactor 106 may undergo one or more post-processing steps downstream of reactor 106.

[0121] d. Single reactor method – post-treatment

[0122] For the hydrogenation reaction in step (i) using each catalyst / support combination (per row) in Table 1 in a single-reactor method, the product stream 108 from reactor 106 is subsequently fed into multiple distillation columns to remove unwanted byproducts and other impurities from the hydrogenation reaction. Each distillation column operates at a pressure ranging from 0 psig to 300 psig. The temperature of the distillation column is determined by the selected pressure.

[0123] The product stream 108 from reactor 106 is fed through a first distillation column 110 to recover unreacted hydrogen (H2). The overhead stream 112 containing hydrogen (H2) can be removed from distillation column 110, or alternatively, it can be fed back to reactor 106 via stream 114, and the bottom stream 116 containing a product mixture comprising 1,1,2-trifluoroethane (HFC-143) is fed to a second distillation column 118.

[0124] The second distillation column 118 is configured to remove hydrogen chloride (HCl) and ethane (HC-170) from the product mixture in the bottom stream 116 from the first distillation column 110. The overhead stream 120 from distillation column 118 contains hydrogen chloride (HCl) and ethane (HC-170), and the bottom stream 122 containing 1,1,2-trifluoroethane (HFC-143) is conveyed to a scrubber 124 to remove hydrogen fluoride (HF). Stream 126 exits the scrubber 124, passes through an optional drying column (not shown), and then enters a third distillation column 128, which is configured to remove low-boiling compounds such as 1,1-difluoroethane (HFC-152a), 1-chloro-1,2-difluoroethane (HCFC-142b), trifluoroethylene (HFO-1123), and 1,1,1-trifluoroethane (HFC-143a). Advantageously, undesirable byproducts HCFC-142 isomers (e.g., 1-chloro-1,2-difluoroethane (HCFC-142a), 1-chloro-2,2-difluoroethane (HCFC-142), and / or 1-chloro-1,1-difluoroethane (HCFC-142b)) and / or chloroethane (HCC-160) can be converted into ethane, R-152, and other low-boiling molecules, and thus will be more easily removed by distillation using distillation column 128.

[0125] The overhead feed stream 130 exits the third distillation column 128 and contains byproduct components such as 1,1-difluoroethane (HFC-152a), HCFC-142 isomers (e.g., 1-chloro-1,2-difluoroethane (HCFC-142a) and / or 1-chloro-2,2-difluoroethane (HCFC-142)) and / or 1,1,1-trifluoroethane (HFC-143a).

[0126] The bottom stream 132 containing 1,1,2-trifluoroethane (HFC-143) is fed into the fourth distillation column 134, from which the top stream 136 containing the desired product 1,1,2-trifluoroethane (HFC-143) is withdrawn.

[0127] e. Single reactor method – desired product

[0128] For the hydrogenation reaction of step (i) in a single-reactor method using each catalyst / support combination (each row) in Table 1, the amount or purity of 1,1,2-trifluoroethane (HFC-143) in the overhead stream 136 from column 134 may be, for example, at least 88 mol%, at least 89 mol%, at least 90 mol%, or at least 91 mol%, based on the total moles of organic components in the composition, and for each of the foregoing, less than or equal to 100 mol.

[0129] For the hydrogenation reaction in step (i) using each catalyst / support combination (per row) in Table 1 in a single-reactor method, the amount of 1-chloro-1,1,2-trifluoroethane (HCFC-133b) in the overhead stream 136 can be, for example, less than 2000 ppm, less than 1000 ppm, less than 500 ppm, or less than 250 ppm, based on the total moles of organic components in the composition.

[0130] f. Single-reactor approach – recycling of desired intermediates

[0131] For the hydrogenation reaction in step (i) using each catalyst / support combination (each row) in Table 1 in the single-reactor method, the bottom recirculation stream 138 from the fourth distillation column 134, containing desired intermediates such as 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 1-chloro-1,2,2-trifluoroethane (HCFC-133), and / or 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a), can be recycled back to reactor 106 via inlet stream 104, so that the aforementioned molecules can be further reacted in a continuous manner according to the single-reactor method of the invention.

[0132] g. Single reactor method – product composition

[0133] For the hydrogenation reaction in step (i) using the single-reactor method with each catalyst / support combination (per row) in Table 1, refer to Figure 1 Based on the total number of moles of the organic components in the composition, the amount of 1,1,2-trifluoroethane (HFC-143) in the product composition from the feed stream 108 of reactor 106 may be, for example, at least 40 mol%, at least 60 mol%, or at least 70 mol%, and for each of the foregoing, less than or equal to 100 mol.

[0134] For the hydrogenation reaction in step (i) using the single-reactor method with each catalyst / support combination (per row) in Table 1, refer to Figure 1 Based on the total number of moles of the organic components in the composition, the amount of 1-chloro-1,1,2-trifluoroethane (HCFC-133b) (if present) in the product composition from the feed stream 108 of reactor 106 may be, for example, greater than or equal to 0.5%, but less than 40 mol%, less than 30 mol%, less than 25 mol%, or less than 20 mol.

[0135] For the hydrogenation reaction in step (i) using the single-reactor method with each catalyst / support combination (per row) in Table 1, refer to Figure 1Based on the total number of moles of the organic components in the composition, the amount of 1-chloro-1,2,2-trifluoroethane (HCFC-133) (if present) in the product composition from the feed stream 108 of reactor 106 may, for example, be greater than or equal to 0.1 mol%, but less than 10 mol%, less than 5 mol%, or less than 1 mol.

[0136] For the hydrogenation reaction in step (i) using the single-reactor method with each catalyst / support combination (per row) in Table 1, refer to Figure 1 Based on the total number of moles of the organic components in the composition, the amount of 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a) (if present) in the product composition from the feed stream 108 of reactor 106 may, for example, be greater than or equal to 0.1 mol%, but less than 15 mol%, less than 5 mol%, or less than 0.5 mol%.

[0137] For the hydrogenation reaction in step (i) using the single-reactor method with each catalyst / support combination (per row) in Table 1, refer to Figure 1 Based on the total molar number of the organic components in the composition, the total amount of 1,1,2-trifluoroethane (HFC-143), 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 1-chloro-1,2,2-trifluoroethane (HCFC-133) and 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a) in the product composition from the feed stream 108 of reactor 106 can be, for example, at least 80 mol%, at least 85 mol%, or at least 90 mol%, and for each of the foregoing, less than or equal to 100 mol.

[0138] For example, for the hydrogenation reaction in step (i) using a single-reactor method with each catalyst / support combination (per row) in Table 1, refer to Figure 1 In the product composition from the feed stream 108 of reactor 106, based on the total combined molar number of HFC-143, HCFC-133b, HCFC-133 and HCFC-123a in the product composition, the amount of 1,1,2-trifluoroethane (HFC-143) may be at least 45 mol% and less than or equal to 99.3 mol%, the amount of 1-chloro-1,1,2-trifluoroethane (HCFC-133b) may be at least 0.5 mol% and less than or equal to 40 mol%, the amount of 1-chloro-1,2,2-trifluoroethane (HCFC-133) may be at least 0.1 mol% and less than or equal to 5 mol%, and the amount of 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a) may be at least 0.1 mol% and less than or equal to 10 mol.

[0139] The combined amount of HFC-143, HCFC-133b, HCFC-133 and HCFC-123 in the composition described in the preceding paragraph may be at least 80 mol% and less than or equal to 100% of the total moles of the organic components of the product composition from the feed stream 108 of reactor 106, while the combined amount of other components containing undesirable byproducts (e.g., HFC-143a, HC-170, HCC-160, HFC-152a and HCFC-142 isomers) may be greater than or equal to 0 mol% and less than 20 mol% of the total moles of the organic components of the product composition from the feed stream 108 of reactor 106.

[0140] For example, for the hydrogenation reaction in step (i) using a single-reactor method with each catalyst / support combination (per row) in Table 1, refer to Figure 1 In the product composition from the feed stream 108 of reactor 106, based on the total combined molar number of HFC-143, HCFC-133b, HCFC-133 and HCFC-123a in the product composition, the amount of 1,1,2-trifluoroethane (HFC-143) may be at least 65 mol% and less than or equal to 99.3 mol%, the amount of 1-chloro-1,1,2-trifluoroethane (HCFC-133b) may be at least 0.5 mol% and less than or equal to 25 mol%, the amount of 1-chloro-1,2,2-trifluoroethane (HCFC-133) may be at least 0.1 mol% and less than or equal to 5 mol%, and the amount of 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a) may be at least 0.1 mol% and less than or equal to 5 mol.

[0141] The combined amount of HFC-143, HCFC-133b, HCFC-133 and HCFC-123 in the composition described in the preceding paragraph may be at least 85 mol% and less than or equal to 100% of the total moles of the organic components of the product composition from the feed stream 108 of reactor 106, while the combined amount of other components containing undesirable byproducts (e.g., HFC-143a, HC-170, HCC-160, HFC-152a and HCFC-142 isomers) may be greater than or equal to 0 mol% and less than 15 mol% of the total moles of the organic components of the product composition from the feed stream 108 of reactor 106.

[0142] For example, for the hydrogenation reaction in step (i) using a single-reactor method with each catalyst / support combination (per row) in Table 1, refer to Figure 1In the product composition from the feed stream 108 of reactor 106, based on the total combined molar number of HFC-143, HCFC-133b, HCFC-133 and HCFC-123a in the product composition, the amount of 1,1,2-trifluoroethane (HFC-143) may be at least 78.5 mol% and less than or equal to 99.3 mol%, the amount of 1-chloro-1,1,2-trifluoroethane (HCFC-133b) may be at least 0.5 mol% and less than or equal to 20 mol%, the amount of 1-chloro-1,2,2-trifluoroethane (HCFC-133) may be at least 0.1 mol% and less than or equal to 1 mol%, and the amount of 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a) may be at least 0.1 mol% and less than or equal to 0.5 mol%.

[0143] The combined amount of HFC-143, HCFC-133b, HCFC-133 and HCFC-123 in the composition described in the preceding paragraph may be at least 90 mol% and less than or equal to 100% of the total moles of the organic components of the product composition from the feed stream 108 of reactor 106, while the combined amount of other components containing undesirable byproducts (e.g., HFC-143a, HC-170, HCC-160, HFC-152a and HCFC-142 isomers) may be greater than or equal to 0 mol% and less than 10 mol% of the total moles of the organic components of the product composition from the feed stream 108 of reactor 106.

[0144] h. Single-reactor approach – Composition of the recirculated feed stream

[0145] For the hydrogenation reaction in step (i) using the single-reactor method with each catalyst / support combination (per row) in Table 1, refer to Figure 1 Based on the total number of moles of the organic components in the composition, the amount of 1,1,2-trifluoroethane (HFC-143) (if present) in the recycle stream 138 entering reactor 106 may be, for example, less than 50 mol%, less than 40 mol%, or less than 3 mol%, and for each of the foregoing, greater than or equal to 0.01 mol.

[0146] For the hydrogenation reaction in step (i) using the single-reactor method with each catalyst / support combination (per row) in Table 1, refer to Figure 1 Based on the total number of moles of the organic components in the composition, the amount of 1-chloro-1,1,2-trifluoroethane (HCFC-133b) in the recycle stream 138 entering reactor 106 can be, for example, greater than 20 mol%, greater than 40 mol%, or greater than 60 mol%, and for each of the foregoing, less than or equal to 100 mol.

[0147] For the hydrogenation reaction in step (i) using the single-reactor method with each catalyst / support combination (per row) in Table 1, refer to Figure 1 Based on the total number of moles of the organic components in the composition, the amount of 1-chloro-1,2,2-trifluoroethane (HCFC-133) (if present) in the recycle stream 138 entering reactor 106 may be, for example, less than 10 mol%, less than 5 mol%, or less than 1 mol%, and for each of the foregoing, greater than or equal to 0.01 mol.

[0148] For the hydrogenation reaction in step (i) using the single-reactor method with each catalyst / support combination (per row) in Table 1, refer to Figure 1 Based on the total number of moles of the organic components in the composition, the amount of 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a) (if present) in the recycle stream 138 entering reactor 106 may be, for example, less than 20 mol%, less than 15 mol%, or less than 9 mol%, and for each of the foregoing, greater than or equal to 0.01 mol.

[0149] For the hydrogenation reaction in step (i) using the single-reactor method with each catalyst / support combination (per row) in Table 1, refer to Figure 1 Based on the total molar number of the organic components in the composition, the total amount of 1,1,2-trifluoroethane (HFC-143), 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 1-chloro-1,2,2-trifluoroethane (HCFC-133) and 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a) in the recycle stream 138 entering reactor 106 may be, for example, at least 80 mol%, at least 90 mol%, or at least 95 mol%, and for each of the foregoing, less than or equal to 100 mol.

[0150] For example, for the hydrogenation reaction in step (i) using a single-reactor method with each catalyst / support combination (per row) in Table 1, refer to Figure 1In the recirculated feed stream 138 entering reactor 106, based on the total combined molar number of HFC-143, HCFC-133b, HCFC-133 and HCFC-123a in the product composition, the amount of 1,1,2-trifluoroethane (HFC-143) can be less than 50 mol% and greater than or equal to 0 mol%, the amount of 1-chloro-1,1,2-trifluoroethane (HCFC-133b) can be at least 20 mol% and less than or equal to 100 mol%, the amount of 1-chloro-1,2,2-trifluoroethane (HCFC-133) can be less than 10 mol% and greater than or equal to 0 mol%, and the amount of 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a) can be less than 20 mol% and greater than or equal to 0 mol%.

[0151] The combined amount of HFC-143, HCFC-133b, HCFC-133, and HCFC-123 in the composition described in the preceding paragraph may be at least 80 mol% and less than or equal to 100% of the total moles of the organic components of the product composition entering the recycle stream 138 of reactor 106, while the combined amount of other components containing undesirable byproducts (e.g., HFC-143a, HC-170, HCC-160, HFC-152a, and HCFC-142 isomers) may be greater than or equal to 0 mol% and less than 20 mol% of the total moles of the organic components of the product composition entering the recycle stream 138 of reactor 106.

[0152] For example, for the hydrogenation reaction in step (i) using a single-reactor method with each catalyst / support combination (per row) in Table 1, refer to Figure 1 In the recirculated feed stream 138 entering reactor 106, based on the total combined molar number of HFC-143, HCFC-133b, HCFC-133 and HCFC-123a in the product composition, the amount of 1,1,2-trifluoroethane (HFC-143) can be less than 40 mol% and greater than or equal to 0 mol%, the amount of 1-chloro-1,1,2-trifluoroethane (HCFC-133b) can be greater than 40 mol% and less than or equal to 100 mol%, the amount of 1-chloro-1,2,2-trifluoroethane (HCFC-133) can be less than 5 mol% and greater than or equal to 0 mol%, and the amount of 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a) can be less than 15 mol% and greater than or equal to 0 mol.

[0153] The combined amount of HFC-143, HCFC-133b, HCFC-133, and HCFC-123 in the composition described in the preceding paragraph may be at least 90 mol% and less than or equal to 100% of the total moles of the organic components of the product composition entering the recycle stream 138 of reactor 106, while the combined amount of other components containing undesirable byproducts (e.g., HFC-143a, HC-170, HCC-160, HFC-152a, and HCFC-142 isomers) may be greater than or equal to 0 mol% and less than 10 mol% of the total moles of the organic components of the product composition entering the recycle stream 138 of reactor 106.

[0154] For example, for the hydrogenation reaction in step (i) using a single-reactor method with each catalyst / support combination (per row) in Table 1, refer to Figure 1 In the recirculated feed stream 138 entering reactor 106, based on the total combined molar number of HFC-143, HCFC-133b, HCFC-133 and HCFC-123a in the product composition, the amount of 1,1,2-trifluoroethane (HFC-143) can be less than 30 mol% and greater than or equal to 0 mol%, the amount of 1-chloro-1,1,2-trifluoroethane (HCFC-133b) can be greater than 60 mol% and less than or equal to 100 mol%, the amount of 1-chloro-1,2,2-trifluoroethane (HCFC-133) can be less than 1 mol% and greater than or equal to 0 mol%, and the amount of 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a) can be less than 9 mol% and greater than or equal to 0 mol%.

[0155] The combined amount of HFC-143, HCFC-133b, HCFC-133, and HCFC-123 in the composition described in the preceding paragraph may be at least 95 mol% and less than or equal to 100% of the total moles of the organic components of the product composition entering the recycle stream 138 of reactor 106, while the combined amount of other components containing undesirable byproducts (e.g., HFC-143a, HC-170, HCC-160, HFC-152a, and HCFC-142 isomers) may be greater than or equal to 0 mol% and less than 5 mol% of the total moles of the organic components of the product composition entering the recycle stream 138 of reactor 106.

[0156] ii. Two-reactor method

[0157] In the two-reactor method for the hydrogenation reaction in step (i) using each catalyst / support combination (each row) in Table 1, the overall reaction method is as described above. Figure 1 As stated below, although combined with the following text Figure 2 In some aspects, reaction conditions can be selectively adjusted to maximize the production of desired products and intermediates while minimizing the production of undesirable byproducts, using, for example, two reactors. In the first reactor, hydrogenation can be carried out at a relatively low temperature, followed by optional distillation and acid removal. The product from the first reactor is then reacted again in the second reactor using a two-reactor method.

[0158] For example, refer to Figure 2 The first reactor 206 is fed by a feed stream 200 containing 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) and a feed stream 202 containing hydrogen (H2). In the first reactor 206, CFC-113 can be hydrogenated to produce a first product composition in feed stream 208, which comprises the target product 1,1,2-trifluoroethane (HFC-143), recyclable intermediates such as 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 1-chloro-1,2,2-trifluoroethane (HCFC-133), and / or 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a), unreacted starting materials such as hydrogen (H2), and 1,1,2-trichloro-1,2,2-trifluoroethane. Ethane (CFC-113), and other undesirable byproducts such as ethane (HC-170), 1,1-difluoroethane (HFC-152a), HCFC-142 isomers (e.g., 1-chloro-1,2-difluoroethane (HCFC-142a), 1-chloro-2,2-difluoroethane (HCFC-142) and / or 1-chloro-1,1-difluoroethane (HCFC-142b)), chloroethane (HCC-160), 1,1,1-trifluoroethane (HFC-143a), hydrogen chloride (HCl), and hydrogen fluoride (HF).

[0159] a. Two-reactor method – First reactor temperature

[0160] Refer again Figure 2In the first reactor 206 of the dual-reactor method, the temperature can be as low as about 200°C, about 205°C, about 210°C, about 215°C, about 220°C, about 225°C, about 230°C, about 235°C, about 240°C, about 245°C, or as high as about 255°C, about 260°C, about 265°C, about 270°C, about 275°C, about 280°C, about 285°C, about 290°C, about 295°C, about 300°C, or within any range covered by any two of the foregoing values ​​as endpoints. For example, the reaction temperature can be about 200°C to about 300°C, about 205°C to about 295°C, about 210°C to about 290°C, about 215°C to about 285°C, about 220°C to about 280°C, about 225°C to about 275°C, about 230°C to about 270°C, about 235°C to about 265°C, about 240°C to about 260°C, or about 245°C to about 255°C.

[0161] b. Two-reactor method – catalyst in the first reactor

[0162] Each catalyst / support combination (per row) in Table 1 can be used in the first reactor 206 of the dual-reactor method for carrying out the hydrogenation reaction in step (i). In one example, the hydrogenation reaction in step (i) can be carried out in the first reactor 206 of the dual-reactor method using a palladium metal catalyst (Pd / C) on a carbon catalyst support at a temperature of about 200°C to about 400°C, wherein the Pd loading is about 1% to about 5% by weight of palladium metal based on the combined weight of palladium metal and carbon support.

[0163] In another example, the hydrogenation reaction in step (i) can be carried out in the first reactor 206 of the dual-reactor method using a palladium metal catalyst (Pd / C) on a carbon catalyst support at a temperature of about 220°C to about 400°C, wherein the Pd loading is about 2% to about 4% by weight of palladium metal based on the combined weight of palladium metal and carbon support.

[0164] In another example, the hydrogenation reaction in step (i) can be carried out in the first reactor 206 of the dual-reactor method using a palladium metal catalyst (Pd / C) on a carbon catalyst support at a temperature of about 250°C to about 350°C, wherein the Pd loading is about 4% by weight of palladium metal based on the combined weight of palladium metal and carbon support.

[0165] In another example, the hydrogenation reaction in step (i) can be carried out in the first reactor 206 of the dual-reactor method using a palladium metal catalyst (Pd / alpha(α)-Al2O3) on an α-alumina catalyst support at a temperature of about 150°C to about 350°C, wherein the Pd loading is about 0.1 wt% to about 10 wt% palladium metal based on the combined weight of palladium metal and alumina support.

[0166] In another example, the hydrogenation reaction in step (i) can be carried out in the first reactor 206 of the dual-reactor method using a palladium metal catalyst (Pd / alpha(α)-Al2O3) on an α-alumina catalyst support at a temperature of about 150°C to about 350°C, wherein the Pd loading is about 0.2 wt% to about 5 wt% palladium metal based on the combined weight of palladium metal and alumina support.

[0167] The preferred catalysts and supports, loadings and temperatures discussed above in conjunction with the hydrogenation reaction in step (i) carried out in the first reactor 206 of the dual-reactor method are summarized in Table 11 below.

[0168] Table 11 – Summary of preferred catalysts (Pd, Pt, Rh) on supports (carbon, α-alumina) – Part 1 of the two-reactor method One reactor – step (i) hydrogenation reaction

[0169]

[0170]

[0171] c. Two-reactor method – Composition of the product stream from the first reactor

[0172] For the hydrogenation reaction in step (i) using the dual-reactor method with each catalyst / support combination (per row) in Table 1, refer to Figure 2 Based on the total number of moles of the organic components in the composition, the amount of 1,1,2-trifluoroethane (HFC-143) in the first product stream 208 from the first reactor 206 of the dual-reactor method can be, for example, at least 40 mol%, at least 60 mol%, or at least 70 mol%, and for each of the foregoing, less than or equal to 100 mol.

[0173] For the hydrogenation reaction in step (i) using the dual-reactor method with each catalyst / support combination (per row) in Table 1, refer to Figure 2 Based on the total number of moles of the organic components in the composition, the amount of 1-chloro-1,1,2-trifluoroethane (HCFC-133b) (if present) in the first product stream 208 from the first reactor 206 of the dual-reactor method can be, for example, greater than 0.5%, but less than 40 mol%, less than 30 mol%, less than 25 mol%, or less than 20 mol.

[0174] For the hydrogenation reaction in step (i) using the dual-reactor method with each catalyst / support combination (per row) in Table 1, refer to Figure 2Based on the total number of moles of the organic components in the composition, the amount of 1-chloro-1,2,2-trifluoroethane (HCFC-133) (if present) in the first product stream 208 from the first reactor 206 of the dual-reactor method can be, for example, greater than 0.1 mol%, but less than 10 mol%, less than 5 mol%, or less than 1 mol.

[0175] For the hydrogenation reaction in step (i) using the dual-reactor method with each catalyst / support combination (per row) in Table 1, refer to Figure 2 Based on the total number of moles of the organic components in the composition, the amount of 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a) (if present) in the first product stream 208 from the first reactor 206 of the dual-reactor method can be, for example, greater than 0.1 mol%, but less than 15 mol%, less than 5 mol%, or less than 0.5 mol.

[0176] For the hydrogenation reaction in step (i) using the dual-reactor method with each catalyst / support combination (per row) in Table 1, refer to Figure 2 Based on the total molar number of the organic components in the composition, the total amount of 1,1,2-trifluoroethane (HFC-143), 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 1-chloro-1,2,2-trifluoroethane (HCFC-133) and 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a) in the first product stream 208 from the first reactor 206 of the dual reactor method can be, for example, at least 80 mol%, at least 85 mol%, or at least 90 mol%, and for each of the foregoing, less than or equal to 100 mol.

[0177] For example, for the hydrogenation reaction in step (i) using the dual-reactor method with each catalyst / support combination (per row) in Table 1, refer to Figure 2 In the first product stream 208 from the first reactor 206 of the dual-reactor method, based on the total combined molar number of HFC-143, HCFC-133b, HCFC-133 and HCFC-123a in the product composition, the amount of 1,1,2-trifluoroethane (HFC-143) may be at least 45 mol% and less than or equal to 99.3 mol%, the amount of 1-chloro-1,1,2-trifluoroethane (HCFC-133b) may be at least 0.5 mol% and less than or equal to 40 mol%, the amount of 1-chloro-1,2,2-trifluoroethane (HCFC-133) may be at least 0.1 mol% and less than or equal to 5 mol%, and the amount of 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a) may be at least 0.1 mol% and less than or equal to 10 mol%.

[0178] The combined amount of HFC-143, HCFC-133b, HCFC-133 and HCFC-123 in the composition described in the preceding paragraph may be at least 85 mol% and less than or equal to 100% of the total molar amount of the organic components of the product composition from the feed stream 208 of the first reactor 206, while the combined amount of other components containing undesirable byproducts (e.g., HFC-143a, HC-170, HCC-160, HFC-152a and HCFC-142 isomers) may be greater than or equal to 0 mol% and less than 15 mol% of the total molar amount of the organic components of the product composition from the feed stream 208 of the first reactor 206.

[0179] For example, for the hydrogenation reaction in step (i) using the dual-reactor method with each catalyst / support combination (per row) in Table 1, refer to Figure 2 In the first product stream 208 from the first reactor 206 of the dual-reactor method, based on the total combined molar number of HFC-143, HCFC-133b, HCFC-133 and HCFC-123a in the product composition, the amount of 1,1,2-trifluoroethane (HFC-143) may be at least 65 mol% and less than or equal to 99.3 mol%, the amount of 1-chloro-1,1,2-trifluoroethane (HCFC-133b) may be at least 0.5 mol% and less than or equal to 25 mol%, the amount of 1-chloro-1,2,2-trifluoroethane (HCFC-133) may be at least 0.1 mol% and less than or equal to 5 mol%, and the amount of 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a) may be at least 0.1 mol% and less than or equal to 5 mol%.

[0180] The combined amount of HFC-143, HCFC-133b, HCFC-133 and HCFC-123 in the composition described in the preceding paragraph may be at least 90 mol% and less than or equal to 100% of the total moles of the organic components of the product composition from the feed stream 208 of the first reactor 206, while the combined amount of other components containing undesirable byproducts (e.g., HFC-143a, HC-170, HCC-160, HFC-152a and HCFC-142 isomers) may be greater than or equal to 0 mol% and less than 10 mol% of the total moles of the organic components of the product composition from the feed stream 208 of the first reactor 206.

[0181] For example, for the hydrogenation reaction in step (i) using the dual-reactor method with each catalyst / support combination (per row) in Table 1, refer to Figure 2In the first product stream 208 from the first reactor 206 of the dual-reactor method, based on the total combined molar number of HFC-143, HCFC-133b, HCFC-133 and HCFC-123a in the product composition, the amount of 1,1,2-trifluoroethane (HFC-143) may be at least 78.5 mol% and less than or equal to 99.3 mol%, the amount of 1-chloro-1,1,2-trifluoroethane (HCFC-133b) may be at least 0.5 mol% and less than or equal to 20 mol%, the amount of 1-chloro-1,2,2-trifluoroethane (HCFC-133) may be at least 0.1 mol% and greater than or equal to 1 mol%, and the amount of 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a) may be greater than 0.1 mol% and less than 0.5 mol%.

[0182] The combined amount of HFC-143, HCFC-133b, HCFC-133 and HCFC-123 in the composition described in the preceding paragraph may be at least 95 mol% and less than or equal to 100% of the total molar amount of the organic components of the product composition from the feed stream 208 of the first reactor 206, while the combined amount of other components containing undesirable byproducts (e.g., HFC-143a, HC-170, HCC-160, HFC-152a and HCFC-142 isomers) may be greater than or equal to 0 mol% and less than 5 mol% of the total molar amount of the organic components of the product composition from the feed stream 208 of the first reactor 206.

[0183] As discussed below, the product from the first reactor 206 may need to undergo one or more post-processing steps downstream of the first reactor 206 before entering the second reactor 240 of the dual-reactor process.

[0184] d. Two-reactor method – Post-treatment of the first reactor

[0185] Refer again Figure 2 In the two-reactor process, the first product stream 208 from the first product stream 206 may optionally be distilled and / or subjected to acid removal before being fed into the second reactor 240 to improve purity and prevent catalyst contamination in any subsequent reactions. See again Figure 2 The first product stream 208 enters the distillation column 210 to remove unreacted hydrogen (H2) via the top stream 212. Alternatively, the top stream 214 containing hydrogen (H2) can be transferred from the distillation column 210 back to the reactor 206.

[0186] The bottom stream 216 is then fed to a second distillation column 218 to remove hydrogen chloride (HCl) and ethane (HC-170). The second distillation column 218 produces an overhead stream 220 containing hydrogen chloride (HCl) and ethane (HC-170) and a bottom stream 222 containing 1,1,2-trifluoroethane (HFC-143), which is then fed to a caustic alkali scrubber 224 to remove hydrogen fluoride (HF). Optionally, the overhead stream 220 containing HCl can be further processed / purified to produce a commercially viable HCl product. Optionally, stream 226 can be dried, for example, using a solid adsorbent such as a 3A / 4A molecular sieve.

[0187] A substantially acid-free feed stream 226 exits the caustic alkali scrubber 224 and enters the third distillation column 228 to remove low-boiling molecules. The distillation column 228 produces an overhead stream 230 containing 1,1-difluoroethane (HFC-152a), HCFC-142 isomers (e.g., 1-chloro-1,2-difluoroethane (HCFC-142a), 1-chloro-2,2-difluoroethane (HCFC-142), and / or 1-chloro-1,1-difluoroethane (HCFC-142b)), 1,1,2-trifluoroethylene (HFO-1123), and 1,1,1-trifluoroethane (HFC-143a), and a bottom stream 232 containing 1,1,2-trifluoroethane (HFC-143).

[0188] The bottom stream 232 is then fed into the fourth distillation column 234. The top stream 236 exits the distillation column 234 and contains the desired product 1,1,2-trifluoroethane (HFC-143), which is removed from the system.

[0189] e. Two-reactor method – Composition of overhead feed 236

[0190] For the hydrogenation reaction in step (i) using the dual-reactor method with each catalyst / support combination (per row) in Table 1, refer to Figure 2 Based on the total number of moles of organic components in the composition, the amount of 1,1,2-trifluoroethane (HFC-143) in the overhead feed 236 can be, for example, greater than 88 mol%, greater than 89 mol%, greater than 90 mol%, or greater than 91 mol%, and for each of the foregoing, less than or equal to 100 mol.

[0191] For the hydrogenation reaction in step (i) using the dual-reactor method with each catalyst / support combination (per row) in Table 1, refer to Figure 2Based on the total number of moles of organic components in the composition, the amount of 1-chloro-1,1,2-trifluoroethane (HCFC-133b) (if present) in the overhead feed 236 can be, for example, less than 2000 ppm, less than 1000 ppm, less than 500 ppm or less than 250 ppm, and for each of the foregoing, greater than or equal to 0 ppm.

[0192] f. Two-reactor method – Composition of bottom feed 238

[0193] For the hydrogenation reaction in step (i) using the dual-reactor method with each catalyst / support combination (per row) in Table 1, refer to Figure 2 Based on the total number of moles of the organic components in the composition, the amount of 1,1,2-trifluoroethane (HFC-143) (if present) in the bottom stream 238 from the fourth distillation column 234 may be, for example, less than 50 mol%, less than 20 mol%, or less than 10 mol%, and for each of the foregoing, greater than or equal to 0.01 mol.

[0194] For the hydrogenation reaction in step (i) using the dual-reactor method with each catalyst / support combination (per row) in Table 1, refer to Figure 2 Based on the total number of moles of the organic components in the composition, the amount of 1-chloro-1,1,2-trifluoroethane (HCFC-133b) in the bottom stream 238 from the fourth distillation column 234 can be, for example, greater than 50 mol%, greater than 60 mol%, or greater than 70 mol%, and for each of the foregoing, less than or equal to 100 mol.

[0195] For the hydrogenation reaction in step (i) using the dual-reactor method with each catalyst / support combination (per row) in Table 1, refer to Figure 2 Based on the total number of moles of the organic components in the composition, the amount of 1-chloro-1,2,2-trifluoroethane (HCFC-133) (if present) in the bottom stream 238 from the fourth distillation column 234 may be, for example, less than 20 mol%, less than 10 mol%, or less than 1 mol%, and for each of the foregoing, greater than or equal to 0.01 mol.

[0196] For the hydrogenation reaction in step (i) using the dual-reactor method with each catalyst / support combination (per row) in Table 1, refer to Figure 2 Based on the total number of moles of the organic components in the composition, the amount of 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a) (if present) in the bottom stream 238 from the fourth distillation column 234 may be, for example, less than 30 mol%, less than 20 mol%, or less than 10 mol%, and for each of the foregoing, greater than or equal to 0.01 mol.

[0197] For the hydrogenation reaction in step (i) using the dual-reactor method with each catalyst / support combination (per row) in Table 1, refer to Figure 2 Based on the total molar number of the organic components in the composition, the total amount of 1,1,2-trifluoroethane (HFC-143), 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 1-chloro-1,2,2-trifluoroethane (HCFC-133) and 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a) in the bottom stream 238 from the fourth distillation column 234 may be, for example, at least 80 mol%, at least 90 mol%, or at least 95 mol%, and for each of the foregoing, less than or equal to 100 mol.

[0198] For example, for the hydrogenation reaction in step (i) using the dual-reactor method with each catalyst / support combination (per row) in Table 1, refer to Figure 2 In the bottom stream 238 from the fourth distillation column 234, based on the total combined molar number of HFC-143, HCFC-133b, HCFC-133 and HCFC-123a in the product composition, the amount of 1,1,2-trifluoroethane (HFC-143) can be less than 50 mol% and greater than or equal to 0 mol%, the amount of 1-chloro-1,1,2-trifluoroethane (HCFC-133b) can be at least 20 mol% and less than or equal to 100 mol%, the amount of 1-chloro-1,2,2-trifluoroethane (HCFC-133) can be less than 10 mol% and greater than or equal to 0 mol%, and the amount of 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a) can be less than 20 mol% and greater than or equal to 0 mol.

[0199] The combined amount of HFC-143, HCFC-133b, HCFC-133 and HCFC-123a in the composition described in the preceding paragraph may be at least 85 mol% and less than or equal to 100% of the total molar amount of the organic components of the product composition from the bottom stream 238 of the fourth distillation column 234, while the combined amount of other components containing undesirable byproducts (e.g., HFC-143a, HC-170, HCC-160, HFC-152a and HCFC-142 isomers) may be greater than or equal to 0 mol% and less than 15 mol% of the total molar amount of the organic components of the product composition from the bottom stream 238 of the fourth distillation column 234.

[0200] For example, for the hydrogenation reaction in step (i) using the dual-reactor method with each catalyst / support combination (per row) in Table 1, refer to Figure 2In the bottom stream 238 from the fourth distillation column 234, based on the total combined molar number of HFC-143, HCFC-133b, HCFC-133 and HCFC-123a in the product composition, the amount of 1,1,2-trifluoroethane (HFC-143) can be less than 40 mol% and greater than or equal to 0 mol%, the amount of 1-chloro-1,1,2-trifluoroethane (HCFC-133b) can be greater than 40 mol% and less than or equal to 100 mol%, the amount of 1-chloro-1,2,2-trifluoroethane (HCFC-133) can be less than 5 mol% and greater than or equal to 0 mol%, and the amount of 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a) can be less than 15 mol% and greater than or equal to 0 mol.

[0201] The combined amount of HFC-143, HCFC-133b, HCFC-133 and HCFC-123a in the composition described in the preceding paragraph may be at least 90 mol% and less than or equal to 100% of the total molar amount of the organic components of the product composition from the bottom stream 238 of the fourth distillation column 234, while the combined amount of other components containing undesirable byproducts (e.g., HFC-143a, HC-170, HCC-160, HFC-152a and HCFC-142 isomers) may be greater than or equal to 0 mol% and less than 10 mol% of the total molar amount of the organic components of the product composition from the bottom stream 238 of the fourth distillation column 234.

[0202] For example, for the hydrogenation reaction in step (i) using the dual-reactor method with each catalyst / support combination (per row) in Table 1, refer to Figure 2 In the bottom stream 238 from the fourth distillation column 234, based on the total combined molar number of HFC-143, HCFC-133b, HCFC-133 and HCFC-123a in the product composition, the amount of 1,1,2-trifluoroethane (HFC-143) can be less than 30 mol% and greater than or equal to 0 mol%, the amount of 1-chloro-1,1,2-trifluoroethane (HCFC-133b) can be greater than 60 mol% and less than or equal to 100 mol%, the amount of 1-chloro-1,2,2-trifluoroethane (HCFC-133) can be less than 1 mol% and greater than or equal to 0 mol%, and the amount of 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a) can be less than 9 mol% and greater than or equal to 0 mol.

[0203] The combined amount of HFC-143, HCFC-133b, HCFC-133 and HCFC-123a in the composition described in the preceding paragraph may be at least 95 mol% and less than or equal to 100% of the total molar amount of the organic components of the product composition from the bottom stream 238 of the fourth distillation column 234, while the combined amount of other components containing undesirable byproducts (e.g., HFC-143a, HC-170, HCC-160, HFC-152a and HCFC-142 isomers) may be greater than or equal to 0 mol% and less than 5 mol% of the total molar amount of the organic components of the product composition from the bottom stream 238 of the fourth distillation column 234.

[0204] g. Two-reactor method – hydrogenation in a second reactor

[0205] For the hydrogenation reaction in step (i) using the dual-reactor method with each catalyst / support combination (per row) in Table 1, refer to Figure 2 The bottom stream 238 from the fourth distillation column 234 is mixed with hydrogen from the stream 244 and then fed into the second reactor 240 of the dual reactor method for the second hydrogenation reaction.

[0206] Although the bottom stream 238 from the fourth distillation column 234 can be directly recycled back to reactor 206, it has been found that stream 238 can be further reacted in the second reactor 240 in a two-reactor process to further enhance the conversion and thus improve the selectivity for the desired product and the desired intermediate.

[0207] h. Two-reactor method – temperature of the second reactor

[0208] For the hydrogenation reaction in step (i) using the dual-reactor method with each catalyst / support combination (per row) in Table 1, refer to Figure 2The second reactor 240 of the dual-reactor method can be operated at temperatures as low as about 200°C, about 205°C, about 210°C, about 215°C, about 220°C, about 225°C, about 230°C, about 235°C, about 240°C, about 245°C, about 250°C, about 255°C, or as high as about 260°C, about 265°C, about 270°C, about 275°C, about 280°C, about 285°C, about 290°C, about 295°C, about 300°C, about 305°C, about 310°C, about 315°C, about 320°C, about 325°C, or within any range covered by any two of the foregoing values ​​as endpoints. For example, the reaction temperature can be about 200°C to about 325°C, about 205°C to about 320°C, about 210°C to about 315°C, about 215°C to about 310°C, about 220°C to about 305°C, about 225°C to about 300°C, about 230°C to about 295°C, about 235°C to about 290°C, about 240°C to about 285°C, about 245°C to about 280°C, about 250°C to about 275°C, about 255°C to about 270°C, or about 260°C to about 265°C.

[0209] i. Two-reactor method – catalyst for the second reactor

[0210] The hydrogenation reaction in step (i) can be carried out in the second reactor of the dual-reactor method using each catalyst / support combination (per row) in Table 1. In one example, the hydrogenation reaction in step (i) in the second reactor 240 of the dual-reactor method can be carried out using a palladium metal catalyst (Pd / C) on a catalyst support at a temperature of about 200°C to about 450°C, wherein the Pd loading is about 1% to about 5% by weight of palladium metal based on the combined weight of palladium metal and carbon support.

[0211] In another example, the hydrogenation reaction in step (i) of the second reactor 240 of the dual-reactor method can be carried out at a temperature of about 220°C to about 400°C using a palladium metal catalyst (Pd / C) on a catalyst support, wherein the Pd loading is about 2% to about 4% by weight of palladium metal based on the combined weight of palladium metal and carbon support.

[0212] In another example, the hydrogenation reaction in step (i) of the second reactor 240 of the dual-reactor method can be carried out at a temperature of about 250°C to about 350°C using a palladium metal catalyst (Pd / C) on a catalyst support, wherein the Pd loading is about 4% by weight of palladium metal based on the combined weight of palladium metal and carbon support.

[0213] In another example, the hydrogenation reaction in step (i) of the second reactor 240 of the dual-reactor method can be carried out at a temperature of about 150°C to about 350°C using a palladium metal catalyst (Pd / alpha(α)-Al2O3) on an α-alumina catalyst support, wherein the Pd loading is about 0.1 wt% to about 10 wt% of palladium metal based on the combined weight of palladium metal and alumina support.

[0214] In another example, the hydrogenation reaction in step (i) of the second reactor 240 of the dual-reactor method can be carried out at a temperature of about 150°C to about 350°C using a palladium metal catalyst (Pd / alpha(α)-Al2O3) on an α-alumina catalyst support, wherein the Pd loading is about 0.2 wt% to about 5 wt% palladium metal based on the combined weight of palladium metal and alumina support.

[0215] For step (i) hydrogenation in the second reactor 240 of the dual-reactor method, the catalyst can be palladium metal (Pd / C) on a carbon support. The catalyst loading can be relatively high to facilitate the conversion of less reactive intermediates. For example, based on the combined weight of palladium metal and carbon support, the Pd loading can be from about 1 wt% to about 5 wt% of palladium metal, such as about 1 wt%, about 2 wt%, about 3 wt%, about 4 wt%, or about 5 wt% of palladium metal.

[0216] For step (i) hydrogenation in the second reactor 240 of the dual-reactor method, the catalyst may be palladium metal on an α-alumina support (Pd / alpha(α)-Al2O3). Based on the combined weight of palladium metal and alumina support, the Pd catalyst loading may be from about 0.1 wt% to about 10 wt% palladium metal, or from about 0.2 wt% to about 5 wt% palladium metal.

[0217] The preferred catalysts and supports, loadings and temperatures for the second reactor 240 used in the dual-reactor method, as discussed above, are summarized in Table 12 below.

[0218] Table 12 – Summary of Catalysts (Pd, Pt, Rh) on Supports (Carbon, α-Alumina) – Second Reaction of the Two-Reactor Method apparatus – step (i) hydrogenation reaction

[0219]

[0220]

[0221] j. Two-reactor method – Composition of the product stream from the second reactor

[0222] Refer again Figure 2The second product stream 242 exits from the second reactor 240 of the dual-reactor method and contains the desired product 1,1,2-trifluoroethane (HFC-143); the desired intermediates 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 1-chloro-1,2,2-trifluoroethane (HCFC-133), and 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a); and the undesirable byproduct isomers of HCFC-142 (e.g., The product stream 242 may be fed to distillation column 210, where it may be optionally distilled and / or acid-removed to improve purity. The product stream contains 1-chloro-1,2-difluoroethane (HCFC-142a), 1-chloro-2,2-difluoroethane (HCFC-142) and / or 1-chloro-1,1-difluoroethane (HCFC-142b), chloroethane (HCC-160), ethane (HC-170), 1,1-difluoroethane (HFC-152a), 1,1,1-trifluoroethane (HFC-143a), hydrogen chloride (HCl), hydrogen fluoride (HF), and unreacted hydrogen (H2).

[0223] For the hydrogenation reaction in step (i) using the dual-reactor method with each catalyst / support combination (per row) in Table 1, refer to Figure 2 Based on the total number of moles of the organic components in the composition, the amount of 1,1,2-trifluoroethane (HFC-143) in the product composition of the second product stream 242 from the second reactor 240 of the dual reactor method can be, for example, at least 40 mol%, at least 50 mol%, or at least 60 mol.

[0224] For the hydrogenation reaction in step (i) using the dual-reactor method with each catalyst / support combination (per row) in Table 1, refer to Figure 2 Based on the total number of moles of the organic components in the composition, the amount of 1-chloro-1,1,2-trifluoroethane (HCFC-133b) (if present) in the product composition of the second product stream 242 from the second reactor 240 of the dual reactor method can be, for example, greater than 0.5 mol%, but less than 40 mol%, less than 20 mol%, or less than 10 mol%.

[0225] For the hydrogenation reaction in step (i) using the dual-reactor method with each catalyst / support combination (per row) in Table 1, refer to Figure 2 Based on the total number of moles of the organic components in the composition, the amount of 1-chloro-1,2,2-trifluoroethane (HCFC-133) (if present) in the product composition of the second product stream 242 from the second reactor 240 of the dual reactor method can be, for example, greater than 0.05%, but less than 10 mol%, less than 5 mol%, or less than 1 mol.

[0226] For the hydrogenation reaction in step (i) using the dual-reactor method with each catalyst / support combination (per row) in Table 1, refer to Figure 2 Based on the total number of moles of the organic components in the composition, the amount of 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a) (if present) in the product composition of the second product stream 242 from the second reactor 240 of the dual reactor method can be, for example, less than 10 mol%, less than 5 mol%, or less than 0.1 mol%, and for each of the foregoing, greater than or equal to 0.01 mol.

[0227] For the hydrogenation reaction in step (i) using the dual-reactor method with each catalyst / support combination (per row) in Table 1, refer to Figure 2 Based on the total molar number of organic components in the composition, the total amount of 1,1,2-trifluoroethane (HFC-143), 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 1-chloro-1,2,2-trifluoroethane (HCFC-133), and 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a) in the product composition of the second product stream 242 from the second reactor 240 of the dual reactor method can be, for example, at least 70 mol%, at least 80 mol%, or at least 90 mol%, and for each of the foregoing, less than or equal to 100 mol.

[0228] For example, for the hydrogenation reaction in step (i) using the dual-reactor method with each catalyst / support combination (per row) in Table 1, refer to Figure 2 In the product composition of the second product stream 242 from the second reactor 240 of the dual-reactor method, based on the total combined molar number of HFC-143, HCFC-133b, HCFC-133 and HCFC-123a in the product composition, the amount of 1,1,2-trifluoroethane (HFC-143) may be at least 40 mol% and less than or equal to 99.45 mol%, the amount of 1-chloro-1,1,2-trifluoroethane (HCFC-133b) may be at least 0.5 mol% and less than or equal to 40 mol%, the amount of 1-chloro-1,2,2-trifluoroethane (HCFC-133) may be at least 0.05 mol% and less than or equal to 10 mol%, and the amount of 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a) may be less than 10 mol% and greater than or equal to 0 mol.

[0229] The combined amount of HFC-143, HCFC-133b, HCFC-133 and HCFC-123a in the composition described in the preceding paragraph may be at least 70 mol% and less than or equal to 100% of the total molar amount of the organic components of the product composition from the second product stream 242 of the second reactor 240 of the dual reactor method, while the combined amount of other components containing undesirable byproducts (e.g., HFC-143a, HC-170, HCC-160, HFC-152a and HCFC-142 isomers) may be greater than or equal to 0 mol% and less than 30 mol% of the total molar amount of the organic components of the product composition from the second product stream 242 of the second reactor 240 of the dual reactor method.

[0230] For example, for the hydrogenation reaction in step (i) using the dual-reactor method with each catalyst / support combination (per row) in Table 1, refer to Figure 2 In the product composition of the second product stream 242 from the second reactor 240 of the dual-reactor method, based on the total combined molar number of HFC-143, HCFC-133b, HCFC-133 and HCFC-123a in the product composition, the amount of 1,1,2-trifluoroethane (HFC-143) may be at least 50 mol% and less than or equal to 99.45 mol%, the amount of 1-chloro-1,1,2-trifluoroethane (HCFC-133b) may be at least 0.5 mol% and less than or equal to 35 mol%, the amount of 1-chloro-1,2,2-trifluoroethane (HCFC-133) may be at least 0.05 mol% and less than or equal to 10 mol%, and the amount of 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a) may be less than 5 mol% and greater than or equal to 0 mol.

[0231] The combined amount of HFC-143, HCFC-133b, HCFC-133 and HCFC-123a in the composition described in the preceding paragraph may be at least 80 mol% and less than or equal to 100% of the total molar amount of the organic components of the product composition from the second product stream 242 of the second reactor 240 of the dual reactor method, while the combined amount of other components containing undesirable byproducts (e.g., HFC-143a, HC-170, HCC-160, HFC-152a and HCFC-142 isomers) may be greater than or equal to 0 mol% and less than 20 mol% of the total molar amount of the organic components of the product composition from the second product stream 242 of the second reactor 240 of the dual reactor method.

[0232] For example, for the hydrogenation reaction in step (i) using the dual-reactor method with each catalyst / support combination (per row) in Table 1, refer to Figure 2 In the product composition of the second product stream 242 from the second reactor 240 of the dual-reactor method, based on the total combined moles of HFC-143, HCFC-133b, HCFC-133 and HCFC-123a in the product composition, the amount of 1,1,2-trifluoroethane (HFC-143) may be at least 60 mol% and less than or equal to 100 mol%, the amount of 1-chloro-1,1,2-trifluoroethane (HCFC-133b) may be at least 0.5 mol% but less than or equal to 30 mol%, the amount of 1-chloro-1,2,2-trifluoroethane (HCFC-133) may be at least 0.05 mol% and less than or equal to 9 mol%, and the amount of 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a) may be less than 1 mol% and greater than or equal to 0 mol.

[0233] The combined amount of HFC-143, HCFC-133b, HCFC-133 and HCFC-123a in the composition described in the preceding paragraph may be at least 90 mol% and less than or equal to 100% of the total molar amount of the organic components of the product composition from the second product stream 242 of the second reactor 240 of the dual reactor method, while the combined amount of other components containing undesirable byproducts (e.g., HFC-143a, HC-170, HCC-160, HFC-152a and HCFC-142 isomers) may be greater than or equal to 0 mol% and less than 10 mol% of the total molar amount of the organic components of the product composition from the second product stream 242 of the second reactor 240 of the dual reactor method.

[0234] k. Two-reactor method – Increase in HFC-143 in the product stream composition provided by the two-reactor method

[0235] Refer again Figure 2 Compared to the bottom stream 238 from the fourth distillation column 234 before entering the second reactor 240, the hydrogenation reaction in the second reactor 240 in the two-reactor process results in an increase in the amount of HFC-143 in the second product stream 242 exiting the second reactor 240. The amount of 1,1,2-trifluoroethane (HFC-143) in the second composition increases by approximately 35 mol% to approximately 130 mol% relative to the amount of 1,1,2-trifluoroethane (HFC-143) in the first composition.

[0236] For the hydrogenation reaction in step (i) using the dual-reactor method with each catalyst / support combination (per row) in Table 1, refer to Figure 2The amount of HFC-143 in the second product stream 242 from the second reactor 240 is increased by at least 35 mol%, at least 40 mol%, or at least 45 mol%, or at least 50 mol%, or at least 60 mol%, or at least 70 mol%, or at least 80 mol%, or at least 90 mol%, or at least 100 mol%, or at least 110 mol%, or at least 120 mol%, and for each of the foregoing, less than or equal to 130 mol%.

[0237] In the process of the present invention according to the single-reactor method or the two-reactor method, undesirable byproducts such as 1,1,1-trifluoroethane (HFC-143a), ethane (HC-170), chloroethane (HCC-160), 1,1-difluoroethane (HFC-152a), and HCFC-142 isomers (e.g., 1-chloro-1,2-difluoroethane (HCFC-142a), 1-chloro-2,2-difluoroethane (HCFC-142), and / or 1-chloro-1,1-difluoroethane (HCFC-142b)) cannot be converted to form 1,1,2-trifluoroethane (HFC-143), and therefore the reaction methods and conditions of the present invention can be adjusted to avoid and / or minimize the formation of such undesirable byproducts.

[0238] IV. Step (ii)

[0239] General process

[0240] The defluorination reaction in step (ii) can be carried out in the vapor phase in a suitable reactor (e.g., a tubular reactor made of a temperature- and / or corrosion-resistant material, such as nickel and its alloys, including Hastelloy (e.g., Hastelloy C276), Inconel (e.g., Inconel 600), Incoloy, and Monel), wherein the vessel may be lined with a fluoropolymer.

[0241] The reactor can first be cleaned and flushed with an inert gas such as nitrogen, and then filled with a catalyst (such as those described below). The catalyst can be pretreated inside the reactor, such as by drying as further described below, before the reactants are metered into the reactor to initiate the reaction.

[0242] The process flow can proceed through the catalyst bed in a downward or upward direction. The reactants can be passed through a scrubber to remove unwanted byproducts such as hydrogen fluoride (HF) and / or hydrogen chloride (HCl) from the reaction, and the reaction products can be collected, for example, by trapping in a cooled cylinder.

[0243] catalyst

[0244] Catalysts and process conditions play an important role in the defluorination reaction.

[0245] Suitable catalysts for the defluorination reaction include metal oxides such as chromium oxide (Cr₂O₃), aluminum oxide (Al₂O₃), iron oxide (Fe₂O₃), and magnesium oxide (MgO). Fluorination of the catalyst can be performed using anhydrous hydrogen fluoride (HF) under conditions that efficiently convert a portion of the metal oxide to the corresponding metal fluoride, such as by the procedure disclosed in U.S. Patent No. 6,780,815 to Cerri et al., the disclosure of which is expressly incorporated herein by reference. Other suitable catalysts for the defluorination reaction include metal fluorides such as chromium fluoride (CrF₃), aluminum oxide fluoride (AlF₃), iron fluoride (FeF₃), magnesium fluoride (MgF₂), and various combinations thereof.

[0246] Other metals (such as Pd, Pt, and Ni) can also be supported on the aforementioned fluorinated metal oxides, for example, by wet impregnation. In this wet impregnation method, the metal salt is exposed to the fluorinated metal oxide support in solution, then dried, and subsequently reduced with hydrogen. Metal catalysts supported on fluorinated metal oxide supports (producing metal fluorides, such as CrF3, AlF3, FeF3, or MgF2) are listed in Table 13 below.

[0247] Table 13 – Supported Metal Catalysts – Step (ii) Defluorination Reaction

[0248]

[0249] Catalyst loading (Pd, Pt, and Ni on CrF3, AlF3, FeF3, or MgF2)

[0250] Based on the total weight of the catalyst and the support, the amount of metal loaded on the support may be about 0.01 wt%, about 0.05 wt%, about 0.1 wt%, about 0.2 wt%, about 0.3 wt%, about 0.4 wt%, about 0.5 wt%, or about 1 wt% to about 2 wt%, about 3 wt%, 5 wt%, 10 wt%, or 20 wt%, or 30 wt%, or 40 wt%, or 50 wt%, or any range covered by two of the foregoing values ​​as endpoints, such as about 0.01 wt% to about 50 wt%, about 0.05 wt% to about 40 wt%, about 0.1 wt% to about 30 wt%, about 0.2 wt% to about 20 wt%, about 0.3 wt% to about 10 wt%, about 0.4 wt% to about 5 wt%, about 0.5 wt% to about 3 wt%, or about 1 wt% to about 2 wt%. For supported noble metal catalysts (such as platinum or palladium), the metal loading can range from about 0.01 wt% to about 5 wt%, preferably from about 0.05 wt% to about 2 wt%, and more preferably from about 0.1 wt% to about 1 wt%. Specific examples of other suitable ranges are shown in Table 14 below.

[0251] Table 14 – Catalyst loading (Pd, Pt, and Ni supported on CrF3, AlF3, FeF3, or MgF2) – Step (ii) Defluorination reaction

[0252]

[0253] When using fluorinated alumina, the amount of metal loaded on the carrier can be from about 0.01% by weight to about 5% by weight, preferably from about 0.05% by weight to about 2% by weight, and most preferably from about 0.1% by weight to about 1% by weight.

[0254] catalyst BET surface area

[0255] The catalyst used in step (ii) can have an appropriate BET (Brunauer, Emmett, and Teller) surface area. The BET surface area of ​​the catalyst can be as low as approximately 10 m². 2 / g, approximately 20m 2 / g, approximately 30m 2 / g, approximately 40m 2 / g, approximately 50m 2 / g, approximately 60m 2 / g, approximately 70m 2 / g, approximately 80m 2 / g, approximately 90m 2 / g, approximately 100m 2 / g, or up to about 110m 2 / g, approximately 120m 2 / g, approximately 130m 2 / g, approximately 140m 2 / g, approximately 150m2 / g, approximately 175m 2 / g, approximately 200m 2 / g, approximately 225m 2 / g, approximately 250m 2 / g, approximately 300m 2 / g, or within any range covered by any of the aforementioned values ​​as endpoints, such as approximately 10m 2 / g to approximately 300m 2 / g, approximately 20m 2 / g to approximately 250m 2 / g, approximately 30m 2 / g to approximately 225m 2 / g, approximately 40m 2 / g to approximately 200m 2 / g, approximately 50m 2 / g to approximately 175m 2 / g, approximately 60m 2 / g to approximately 150m 2 / g, approximately 70m 2 / g to approximately 140m 2 / g, approximately 80m 2 / g to approximately 130m 2 / g, approximately 90m 2 / g to approximately 120m 2 / g or approximately 100mg 2 / g to approximately 110m 2 / g. For metal oxide catalysts, the BET surface area is preferably greater than about 100 m². 2 / g. For fluorinated metal oxide catalysts, the BET surface area is preferably greater than about 20 m². 2 / g. BET analysis is a standard method for determining surface area using nitrogen adsorption isotherms. The BET surface area of ​​the catalyst can be measured using a TriStar II Micromeritics instrument. The catalyst sample is degassed before analysis using a FlowPrep 060 instrument. Specific examples of other suitable ranges are shown in Table 15 below.

[0256] Table 15 – Catalysts (Cr2O3, Al2O3, Fe2O3, MgO, CrF3 supported on CrF3, AlF3, FeF3 or MgF2) BET surface area of ​​AlF3, FeF3, MgF2 or Pd, Pt and Ni – step (ii) dehydrofluorination reaction

[0257]

[0258] When using fluorinated alumina, the surface area of ​​BET can be greater than approximately 10 m². 2 / g, preferably greater than 20m 2 / g, optimal value is greater than 25m 2 / g.

[0259] Catalyst pretreatment

[0260] The catalyst can be pretreated by drying at elevated temperatures, ranging from as low as about 200°C, about 250°C, about 300°C, about 350°C, about 360°C, about 370°C, or as high as about 390°C, about 400°C, about 450°C, about 500°C, about 550°C, about 600°C, or any range encompassed by two of the foregoing values ​​as endpoints, such as about 200°C to about 600°C, about 250°C to about 550°C, about 300°C to about 500°C, about 350°C to about 450°C, about 360°C to about 400°C, or about 370°C to about 390°C. Specific examples of other suitable ranges are shown in Table 16 below.

[0261] Table 16 – Catalysts (Cr2O3, Al2O3, Fe2O3, MgO, CrF3 supported on CrF3, AlF3, FeF3 or MgF2) Pretreatment drying temperature of AlF3, FeF3, MgF2 or Pd, Pt and Ni – Step (ii) defluorination reaction

[0262]

[0263] When using fluorinated alumina, the catalyst can be pretreated by drying at a temperature of about 200°C to about 600°C, preferably about 300°C to about 600°C, and most preferably about 400°C to about 550°C.

[0264] As part of catalyst activation, the catalyst may be exposed to an inert gas, such as N2. The pretreatment process may take as little as about 1 hour, about 2 hours, about 3 hours, about 4 hours, or as long as about 5 hours, about 6 hours, about 10 hours, about 20 hours, or any range covered by two of the foregoing values ​​as endpoints, such as about 1 hour to about 20 hours, about 2 hours to about 10 hours, about 3 hours to about 6 hours, or about 4 hours to about 5 hours.

[0265] When using fluorinated alumina, the pretreatment process can take from about 1 hour to about 10 hours, preferably from about 2 hours to about 6 hours, and most preferably from about 3 hours to about 5 hours.

[0266] Reaction conditions – temperature

[0267] The temperature range for the defluorination reaction can be as low as about 125°C, about 150°C, about 200°C, about 250°C, about 300°C, about 350°C, about 400°C, or about 450°C, or as high as about 500°C, about 550°C, about 600°C, about 650°C, about 700°C, about 750°C, or about 800°C, or any range covered by two of the foregoing values ​​as endpoints, such as about 125°C to about 800°C, about 150°C to about 750°C, about 200°C to about 650°C, about 250°C to about 600°C, about 300°C to about 550°C, about 350°C to about 500°C, or about 400°C to about 450°C. The temperature can preferably be about 250°C to about 450°C, and more preferably about 300°C to about 400°C. Specific examples of other suitable ranges are shown in Table 17 below.

[0268] Table 17 – When using catalysts (Cr2O3, Al2O3, Fe2O3, MgO, etc. supported on CrF3, AlF3, FeF3, or MgF2) The reaction temperature for CrF3, AlF3, FeF3, MgF2 or Pd, Pt and Ni) – step (ii) dehydrofluorination reaction

[0269]

[0270] When using fluorinated alumina, the reaction temperature can be from about 125°C to about 500°C, preferably from about 250°C to about 450°C, and most preferably from about 300°C to about 400°C.

[0271] Reaction conditions – pressure

[0272] The pressure can be as low as about 1 psig, about 2 psig, about 3 psig, about 4 psig, or about 5 psig, about 10 psig, about 15 psig, about 20 psig, about 25 psig, about 30 psig, about 35 psig, about 40 psig, about 50 psig, or any range covered by two of the foregoing values ​​as endpoints, such as about 1 psig to about 50 psig, about 2 psig to about 40 psig, about 3 psig to about 35 psig, about 4 psig to about 25 psig, about 5 psig to about 20 psig, or about 10 psig to about 15 psig. For example, the pressure can be about 1 psig to about 50 psig, preferably about 5 psig to about 30 psig, more preferably about 10 psig to about 20 psig. Specific examples of other suitable ranges are shown in Table 18 below.

[0273] Table 18 – When using catalysts (Cr2O3, Al2O3, Fe2O3, MgO, etc. supported on CrF3, AlF3, FeF3, or MgF2) Reaction pressures for CrF3, AlF3, FeF3, MgF2 or Pd, Pt and Ni – Step (ii) Dehydrofluorination reaction

[0274]

[0275] When using fluorinated alumina, the reaction pressure can be from about 1 psig to about 50 psig, preferably from about 5 psig to about 30 psig, and most preferably from about 10 psig to about 20 psig.

[0276] Reaction conditions – contact time

[0277] The contact time between the reactant and the catalyst can be as short as about 0.1 seconds, about 1 second, about 5 seconds, about 10 seconds, about 15 seconds, or about 20 seconds, or as long as about 25 seconds, about 30 seconds, about 40 seconds, about 50 seconds, about 60 seconds, or about 120 seconds, approximately or within any range encompassed by two of the aforementioned values ​​as endpoints, such as about 0.1 seconds to about 120 seconds, about 1 second to about 60 seconds, about 5 seconds to about 50 seconds, about 10 seconds to about 40 seconds, about 15 seconds to about 30 seconds, or about 20 seconds to about 25 seconds. For example, the contact time can be from about 1 second to about 60 seconds. Specific examples of other suitable ranges are shown in Table 19 below.

[0278] Table 19 – Reactants and Catalysts (Cr2O3, Al2O3, Fe2O3, MgO, etc. supported on CrF3, AlF3, FeF3 or MgF2) Contact time of CrF3, AlF3, FeF3, MgF2 or Pd, Pt and Ni – step (ii) dehydrofluorination reaction

[0279]

[0280] When using fluorinated aluminum oxide, the contact time can be from about 1 second to about 60 seconds, preferably from about 5 seconds to about 40 seconds, and most preferably from about 10 seconds to about 30 seconds.

[0281] Product – cis / trans ratio

[0282] In the defluorination reaction of step (ii), the cis / trans molar ratio of 1,2-difluoroethylene in the product mixture can be as low as about 1, about 2, about 3, about 4, about 5, about 6, about 7, or as high as about 9, about 10, about 11, about 12, about 13, about 14, about 15, or any range covered by two of the foregoing values ​​as endpoints, such as about 1 to about 15, about 2 to about 14, about 3 to about 13, about 4 to about 12, about 5 to about 11, about 6 to about 10, or about 7 to about 9. For example, the cis / trans ratio can be about 2 to about 15.

[0283] When using fluorinated alumina, the cis / trans molar ratio of 1,2-difluoroethylene in the product mixture can be from about 1 to about 15, preferably from about 1 to about 10, and most preferably from about 2 to about 7.

[0284] Product-selectivity

[0285] The desired selectivity of the 1,2-difluoroethylene products (the sum of 1232E and 1232Z) can be as low as about 80%, about 85%, about 89%, about 90%, about 91%, about 92%, or as high as about 94%, about 95%, about 96%, about 97%, about 98%, about 99%, or any range covered by two of the foregoing values ​​as endpoints, such as about 80% to about 99%, about 85% to about 98%, about 89% to about 97%, about 90% to about 96%, about 91% to about 95%, or about 92% to about 94%. Specific examples of other suitable ranges are shown in Table 20 below.

[0286] Table 20 – Catalysts used (Cr2O3, Al2O3, Fe2O3, MgO, CrF3 supported on CrF3, AlF3, FeF3, or MgF2) Selectivity of AlF3, FeF3, MgF2 or Pd, Pt and Ni for the desired product – step (ii) dehydrofluorination reaction

[0287]

[0288] When using fluorinated alumina, the selectivity for the desired 1,2-difluoroethylene products (the sum of 1232E and 1232Z) can be from about 85% to about 99%, preferably from about 90% to about 99%, and most preferably from about 95% to about 99%.

[0289] Product-starting material conversion rate

[0290] The conversion of the starting material to 1,2-difluoroethylene can be greater than about 10%, greater than about 20%, greater than about 30%, greater than about 40%, greater than about 50%, greater than about 60%, greater than about 70%, greater than about 80%, greater than about 90%, greater than about 95%, greater than about 99%, or any range covered by two of the aforementioned values ​​as endpoints, such as about 10% to about 99%, about 20% to about 95%, about 30% to about 80%, about 40% to about 70%, or about 50% to about 60%. Specific examples of other suitable ranges are shown in Table 21 below.

[0291] Table 21 – Starting materials for 1,2-difluoroethylene catalysts (Cr2O3 supported on CrF3, AlF3, FeF3 or MgF2) Conversion rate of Al2O3, Fe2O3, MgO, CrF3, AlF3, FeF3, MgF2 or Pd, Pt and Ni) – Step (ii) Defluorination reaction

[0292]

[0293] When using fluorinated alumina, the conversion rate of the starting material to 1,2-difluoroethylene can be greater than about 20%, preferably greater than about 30%, and most preferably greater than about 60%.

[0294] Catalyst regeneration

[0295] After prolonged use, it may also be advantageous to periodically regenerate the catalyst while it is in place in the reactor. Catalyst regeneration can be accomplished by any means known in the art, for example, by passing air, or air diluted with nitrogen, over the catalyst at a temperature of about 100°C to about 400°C, preferably about 200°C to about 375°C, for about 0.5 hours to about 3 days. This can be followed by hydrogen fluoride treatment (for fluorinated catalysts) at a temperature of about 100°C to about 400°C, preferably about 200°C to about 350°C, or hydrogen treatment (for supported transition metal catalysts) at a temperature of about 100°C to about 400°C, preferably about 200°C to about 350°C.

[0296] When using fluorinated alumina, the catalyst can be regenerated by passing air, or air diluted with nitrogen, over the catalyst at a temperature of about 100°C to about 400°C, preferably about 200°C to about 375°C, for about 0.5 hours to about 3 days. This can be followed by hydrogen fluoride treatment at a temperature of about 100°C to about 400°C, preferably about 200°C to about 350°C. Furthermore, the process of the present invention advantageously avoids and / or minimizes the formation of 1,1,1,-trifluoroethane (HFC-143a), wherein, based on the total molar percentage of the product composition, the product of step (ii) (including trans-1,2-difluoroethylene (HFO-1132E)) may contain less than 5 mol%, less than 3 mol%, less than 1 mol%, less than 0.5 mol%, or less than 0.1 mol% of 1,1,1,-trifluoroethane (HFC-143a).

[0297] Characteristics when the catalyst is fluorinated alumina

[0298] When fluorinated alumina is used as a catalyst, the following characteristics may be present: The amount of metal supported on the support can be from about 0.01 wt% to about 5 wt%, preferably from about 0.05 wt% to about 2 wt%, and most preferably from about 0.1 wt% to about 1 wt%. The BET surface area can be greater than about 10 m². 2 / g, preferably greater than 20m 2 / g, optimal value is greater than 25m 2 / g. The catalyst can be pretreated by drying at a temperature of about 200°C to about 600°C, preferably about 300°C to about 600°C, and most preferably about 400°C to about 550°C. The pretreatment process can take about 1 hour to about 10 hours, preferably about 2 hours to about 6 hours, and most preferably about 3 hours to about 5 hours. The reaction temperature can be about 125°C to about 500°C, preferably about 250°C to about 450°C, and most preferably about 300°C to about 400°C. The reaction pressure can be about 1 psig to about 50 psig, preferably about 5 psig to about 30 psig, and most preferably about 10 psig to about 20 psig. The contact time can be about 1 second to about 60 seconds, preferably about 5 seconds to about 40 seconds, and most preferably about 10 seconds to about 30 seconds. The cis / trans molar ratio of 1,2-difluoroethylene in the product mixture can be about 1 to about 15, preferably about 1 to about 10, and most preferably about 2 to about 7. The selectivity for the desired 1,2-difluoroethylene products (the sum of 1232E and 1232Z) can be from about 85% to about 99%, preferably from about 90% to about 99%, and most preferably from about 95% to about 99%. The conversion of the starting material to 1,2-difluoroethylene can be greater than about 20%, preferably greater than about 30%, and most preferably greater than about 60%. The catalyst can be regenerated by passing air or nitrogen-diluted air over the catalyst at a temperature of about 100°C to about 400°C, preferably from about 200°C to about 375°C, for about 0.5 hours to about 3 days. After this regeneration, hydrogen fluoride treatment can be performed at a temperature of about 100°C to about 400°C, preferably from about 200°C to about 350°C.

[0299] V. Step (iii)

[0300] General process

[0301] The 1,2-difluoroethylene (HFO-1132) obtained in step (ii) above can be produced as a mixture containing both trans-1,2-difluoroethylene (HFO-1132E) and cis-1,2-difluoroethylene (HFO-1132Z) isomers.

[0302] In step (iii), the cis-1,2-difluoroethylene (HFO-1132Z) isomer can be converted to the trans-1,2-difluoroethylene (HFO-1132E) isomer by exposure to heat and / or a catalyst to produce a final product comprising at least 5% by weight of trans-1,2-difluoroethylene (HFO-1232E), at least 10% by weight of trans-1,2-difluoroethylene (HFO-1232E), at least 20% by weight of trans-1,2-difluoroethylene (HFO-1232E), at least 30% by weight of trans-1,2-difluoroethylene (HFO-1232E) or more. The product stream from the isomerization reactor can be further distilled to produce a final product comprising, substantially comprising, or comprising: a high purity trans-1,2-difluoroethylene (HFO-1132E) isomer, wherein the high purity is such as at least about 95% by weight, at least about 99.0% by weight, at least about 99.9% by weight, at least about 99.99% by weight, or higher.

[0303] The isomerization reaction can be carried out in any suitable reaction vessel or reactor, but it should preferably be constructed of a corrosion-resistant material, such as nickel and its alloys, including Hastelloy (e.g., Hastelloy C276), Inconel (e.g., Inconel 600), and Monel), wherein the vessel may be lined with a fluoropolymer. These can be single tubes or multiple tubes filled with the isomerization catalyst.

[0304] Reaction conditions – temperature

[0305] The temperature range for the isomerization reaction can be as low as about 100°C, about 150°C, about 200°C, about 250°C, about 300°C, about 350°C, about 400°C, or as high as about 500°C, about 550°C, about 600°C, about 650°C, about 700°C, about 750°C, about 800°C, or any range covered by two of the aforementioned values ​​as endpoints, such as about 100°C to about 800°C, about 150°C to about 750°C, about 200°C to about 700°C, about 250°C to about 650°C, about 300°C to about 600°C, about 350°C to about 550°C, or about 400°C to about 500°C. Specific examples of other suitable ranges are shown in Table 22 below.

[0306] Table 22 – Reaction Temperature – Step (iii) Isomerization Reaction

[0307]

[0308] Reaction conditions – pressure

[0309] The reaction can be carried out at atmospheric pressure, extra-atmospheric pressure, or vacuum. Vacuum pressures can be approximately 5 Torr, approximately 10 Torr, approximately 25 Torr, approximately 50 Torr, approximately 100 Torr, approximately 150 Torr, approximately 200 Torr, approximately 250 Torr, approximately 300 Torr to approximately 350 Torr, 400 Torr, approximately 450 Torr, approximately 500 Torr, approximately 550 Torr, approximately 600 Torr, approximately 650 Torr, approximately 700 Torr, approximately 760 Torr, or any range using any of the foregoing values ​​as endpoints, such as approximately 5 Torr to approximately 760 Torr, approximately 10 Torr to approximately 700 Torr, approximately 25 Torr to approximately 650 Torr, approximately 50 Torr to approximately 600 Torr, approximately 100 Torr to approximately 550 Torr, approximately 150 Torr to approximately 500 Torr, approximately 200 Torr to approximately 450 Torr, or approximately 250 Torr to approximately 400 Torr, or approximately 300 Torr to approximately 350 Torr. Specific examples of other suitable ranges are shown in Table 23 below.

[0310] Table 23 – Reaction Pressure – Step (iii) Isomerization Reaction

[0311]

[0312] Reaction conditions – contact time

[0313] The contact time between the reactants and the catalyst can be in the range of about 0.5 seconds, about 1 second, about 5 seconds, about 10 seconds to about 20 seconds, about 30 seconds, about 60 seconds, or about 120 seconds, or any range using any of the foregoing values ​​as endpoints, such as about 0.5 seconds to about 120 seconds, about 1 second to about 60 seconds, about 5 seconds to about 30 seconds, or about 10 seconds to about 20 seconds. However, longer or shorter times can be used.

[0314] Reaction conditions – environment

[0315] The reaction can also be carried out in an inert atmosphere in which oxygen is essentially absent. For example, the amount of oxygen present during the reaction can be less than 15% by weight, less than 10% by weight, less than 5% by weight, or less than 1% by weight, or any range using any two of the foregoing values ​​as endpoints, such as about 1% by weight to about 15% by weight, or about 5% by weight to about 10% by weight.

[0316] The reaction can also be carried out in the absence of water. For example, based on the total weight of the reactants in the reactor, the amount of water present during the reaction can be less than 5% by weight, less than 1% by weight, less than 0.5% by weight, or less than 0.05% by weight, or any range using any two of the foregoing values ​​as endpoints, such as 0.05% by weight to about 5% by weight, or about 0.5% by weight to about 1% by weight.

[0317] Example

[0318] Example 1

[0319] In a single-reactor approach, intermediates are reacted to produce HFC-143.

[0320] Example 1 illustrates the conversion using a Pd / C catalyst with a feed containing 17 ± 2% HCFC-123a and 83 ± 2% CFC-113. The purpose of these experiments was to evaluate the ability to recycle reaction intermediates during the conversion of CFC-113 to HFC-143. If the content of HCFC-123a molecules in the product stream is less than that in the feed, the conditions are considered suitable for the recycling of HCFC-123a molecules.

[0321] The experimental setup used included a feed system containing gas flow controllers for N2 and H2 and a micro-motion mass flow meter connected to a research control valve (RCV) that controls the flow of organic matter. The reactor consisted of one-inch 316 SS tubes filled with catalyst. Thermocouples were inserted into the center of the catalyst bed to read the operating temperature. The pressure control system consisted of the RCV, which controlled the pressure by receiving feedback from a pressure transducer placed downstream of the reactor. For GC analysis, samples were collected downstream of the reactor using sample bags filled with approximately 50 g of water to capture hydrogen chloride (HCl) and hydrogen fluoride (HF). Prior to GC analysis, the sample bags were heated at 60°C for one hour to ensure all organic contents were in the gas phase. Samples were then extracted using a syringe and injected into the GC-FID instrument for analysis.

[0322] Table 24 shows the GC-FID area percentage of the product streams for three different catalysts at specified temperatures. The organic feed rate was 10 g / h, the H2 feed rate was 150 ml / min, the catalyst volume was 50 ml, and the pressure was 45 psig.

[0323] As shown in Table 24, at temperatures >225 °C, all catalysts exhibited near-complete conversion of CFC-113, and the HCFC-123a concentration was lower than that in the feed, indicating that the consumption rate of HCFC-123a exceeded its formation rate. The amount of unconverted HCFC-123a decreased with increasing reaction temperature. Based on the GC-FID area percentage, catalysts with higher Pd loadings required lower temperatures to achieve near-complete conversion (>99%) of HCFC-123a. For example, near-complete conversion of HCFC-123a was observed at 250 °C on a 4% Pd / C catalyst, while this conversion was observed at approximately 280 °C on a 2% Pd / C catalyst.

[0324] BET (Brunauer, Emmett, and Teller) analysis is a standard method for determining surface area from nitrogen adsorption isotherms. The BET surface area of ​​the catalyst can be measured using a TriStar II Micromeritics instrument. Prior to BET analysis, the catalyst sample was degassed at 150°C using a FlowPrep 060 instrument. The BET surface area of ​​the 4% Pd / C catalyst in Example 1 was 1661.6 m². 2 / g. The BET surface area of ​​the 2% Pd / C catalyst in Example 1 is 207.7 m². 2 / g. The BET surface area of ​​the 1% Pd / C catalyst in Example 1 is 1042.2 m². 2 / g.

[0325] Table 24

[0326] Using a Pd / C catalyst, for a feed containing 17±2% HCFC-123a and 83±2% CFC-113, the reactor... Subsequent product compositions

[0327]

[0328] Example 1a

[0329] This example demonstrates the conversion of pure CFC-113 and pure HCFC-123a (purity >99%) to HFC-143 at 200°C using a 1% Pd / C catalyst. The reaction setup was the same as in Example 1. Table 25 shows the GC-FID area percentage of the product stream. The organic feed rate was 10 g / h, the H2 feed rate was 150 ml / min, the catalyst volume was 50 ml, and the pressure was 45 psig. Based on the total moles of the organic components in the composition, the conversion of CFC-113 under these conditions was greater than 99.9%. Significant amounts of HCFC-123a, HCFC-133b, and HCFC-133 intermediates were generated, but these intermediates can be recycled. Based on the total moles of the organic components in the composition, the conversion of pure HCFC-123a under these conditions was 8.74%, indicating that HCFC-123a is significantly less reactive than CFC-113. Based on the total molar number of the organic components in the composition, the total amount of undesirable byproducts (including the amount of the major byproduct R-152a) is less than 25% or less than 20%.

[0330] For the data in Table 25, the temperature was 200 ± 1 °C, the pressure was 45 psig, the organic feed rate was 10 g / h, the H2 feed rate was 150 ml / min, and the catalyst volume was 50 ml. The BET surface area of ​​the 1% Pd / C catalyst in Example 1a was 865.4 m². 2 / g.

[0331] Table 25

[0332] Conversion rate using 1% Pd / C, 99.9% pure CFC-113 feed

[0333]

[0334] Example 1b

[0335] This example demonstrates the conversion of a feed containing 17 ± 2% HCFC-123a and 83 ± 2% CFC-113 using Pd / C and Pd / Al2O3 catalysts at temperatures ≤200°C. The reaction setup is similar to that of Example 1. The purpose of these experiments is to evaluate the ability to recycle reaction intermediates during the conversion of CFC-113 to HFC-143. If the content of HCFC-123a molecules in the product stream is less than that in the feed, the conditions are considered suitable for the recycling of HCFC-123a molecules.

[0336] Table 26 shows the GC-FID analysis results (area percentage) of the product feed stream. The organic feed rate was 10 g / h, the H2 feed rate was 150 ml / min, and the reactor pressure was 45 psig. For the 1% Pd / C catalyst, 50 ml of catalyst was used without dilution. For the 0.3% Pd / Sita(θ)-Al2O3 catalyst, 10 ml of catalyst was diluted with 40 ml of 316 SS mesh packing material (1.8 inches). For both catalysts, the CFC-123a content was higher than that of the feed composition at temperatures ≤200°C. These results indicate that at temperatures ≤200°C, the formation rate of HCFC-123a is greater than its consumption rate, and therefore, temperatures >200°C are preferred for recycling HCFC-123a and its conversion to HFC-143.

[0337] For the data in Table 26, the organic feed rate was 10 g / h, the H2 feed rate was 150 ml / min, the catalyst volume was 50 ml, and the pressure was 45 psig. The BET surface area of ​​the 1% Pd / C catalyst in Example 1b was 865.4 m². 2 / g. The BET surface area of ​​the 0.3% Pd / Sita(θ)-Al2O3 catalyst in Example 1b is 38.1 m². 2 / g.

[0338] Table 26

[0339] The conversion rate of a feed containing 17 ± 2% HCFC-123a and 83 ± 2% CFC-113 using a Pd catalyst.

[0340]

[0341] Example 2

[0342] The intermediate is used to carry out a second reaction in a two-reactor process to produce HFC-143.

[0343] This embodiment illustrates the conversion of (HCFC-133b and HCFC-133) / HCFC-123a, which are intermediates in the process of converting CFC-113 to HFC-143 in a two-reactor process.

[0344] After distilling the resulting reaction products, an organic feed is obtained and collected in the first reactor of a two-reactor process, which operates primarily at 200°C or lower. In total, approximately 500 grams of the distillation column overhead distillate is collected in a 1 L SS cylinder. Note that the distillation column overhead distillate initially contains 0.23 wt% hydrogen fluoride (HF) and 0.03 wt% hydrogen chloride (HCl) (analytical procedures are described below); using this feed leads to catalyst deactivation. Therefore, acid removal is necessary.

[0345] The collected distillate from the distillation column was washed through a ½-inch PFA tube filled with a 14-inch CLR-204 for HCl removal, a 9-inch P-188 for HF removal, a 12-inch activated 3A molecular sieve for water removal, and a 3-inch Drierite as a water indicator. The material from the end of the acid removal tube was collected in a separate clean 1L SS cylinder placed in a dry ice bath. The collected product showed no signs of hydrogen chloride (HCl) or hydrogen fluoride (HF), indicating the effectiveness of the acid removal procedure.

[0346] The following procedure is typically used to analyze the material collected in a product collection cylinder (PCC). A known amount of sample (1 to 3 grams) is taken from a Tedlar sample bag containing a known amount of water (approximately 50 grams). After heating the sample bag at 60°C, 0.25 ml of the gas sample is taken using a GC-syringe (also heated in a 60°C oven) and immediately injected into the GC instrument. Ion chromatography (IC) is used to analyze the water content within the Tedlar bag to determine the acid content in the gas.

[0347] The experimental setup for the two-reactor method is similar to that in Example 1 and as follows: Figure 2As shown. 50 ml of 4% Pd / C catalyst was charged into the second reactor 240 of the dual-reactor method. The reaction was carried out at 45 psig, with an organic feed rate of 10 g / h and an H2 feed rate of 150 ml / min. Samples were taken just before the feed flow reached the second reactor 240 of the dual-reactor method, showing the following feed composition (based on GC-FID area percentage): 54.56% 1,1,2-trifluoroethane (HFC-143), 30.58% 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 0.78% 1-chloro-1,2,2-trifluoroethane (HCFC-133), 2.43% 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a), and 3.60% 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113).

[0348] Table 27 shows the GC-FID area percentage of the product stream (i.e., stream 242 after the second reactor 240 in the dual-reactor method). At 250°C, based on the total moles of the organic components in the composition, 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) and 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a) from the feed were almost completely converted, 1-chloro-1,1,2-trifluoroethane (HCFC-133b) was converted at 22%, and the content of 1-chloro-1,2,2-trifluoroethane (HCFC-133) increased slightly. At 280°C, based on the total molar number of organic components in the composition, 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) and 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a) from the feed were almost completely converted, 1-chloro-1,1,2-trifluoroethane (HCFC-133b) was converted at 52%, and 1-chloro-1,2,2-trifluoroethane (HCFC-133) was converted at 72%.

[0349] For the data in Table 27, the organic feed rate was 10 g / h, the H2 feed rate was 150 ml / min, the catalyst volume was 50 ml, and the pressure was 45 psig.

[0350] Table 27

[0351] Using a 4% Pd / C catalyst, containing 54.56% HFC-143, 30.58% HCFC-133b, and 0.78% HCFC-133, Conversion rates of 2.43% HCFC-123a and 3.60% CFC-113 feeds

[0352]

[0353] Example 3

[0354] Single-reactor method for producing HFC-143 from pure CFC-113

[0355] This example demonstrates the conversion of pure CFC-113 to HFC-143 using a 4% Pd / C catalyst at temperatures ≥250°C (in a single-reactor method). The experimental setup was similar to that of Example 1. The organic feed rate was 10 g / h, the H2 feed rate was 150 ml / min, the catalyst volume was 50 ml, and the pressure was 45 psig.

[0356] Table 28 shows the product stream after the reactor (e.g., as shown in Table 28). Figure 1 The GC-FID area percentage of the feed stream 108 following reactor 106 is shown. Based on the total moles of the organic components in the composition, the CFC-113 conversion was 100% at all temperatures. Based on the total moles of the organic components in the composition, the total amount of recyclable reaction intermediates (HCFC-133b and HCFC-133) / HCFC-123a formed with temperature variation was 23.93% at 251°C, 22.78% at 256°C, and 20.21% at 260°C. Less reaction intermediates were formed at higher temperatures. It appears that the reaction intermediates can be further reacted at temperatures >250°C.

[0357] Table 28

[0358] Conversion of pure CFC-113 using 4% Pd / C catalyst as a function of reactor temperature

[0359]

[0360] Example 3a

[0361] This example demonstrates the conversion of pure CFC-113 to HFC-143 at 200°C using a 4% Pd / C catalyst (in a single-reactor method). The experimental setup was similar to that of Example 1. The organic feed rate was 10 g / h, the H2 feed rate was 150 ml / min, the catalyst volume was 50 ml, and the pressure was 45 psig.

[0362] Table 29 shows the product stream after the reactor (e.g., in...). Figure 1 The percentage of GC-FID area in the feed stream 108 following reactor 106 shown. Based on the total moles of the organic components in the composition, the CFC-113 conversion is 100%. Based on the total moles of the organic components in the composition, the total amount of recyclable reaction intermediates (HCFC-133b and HCFC-133) / HCFC-123a formed with temperature variation is 38.29% at 200°C. More reaction intermediates are generated at 200°C.

[0363] Table 29

[0364] The conversion of pure 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) at 200 °C using a 4% Pd / C catalyst. Rate

[0365]

[0366] Example 4

[0367] Single-reactor method for producing HFC-143

[0368] This embodiment illustrates the conversion of CFC-113 to HFC-143 in a single reactor, and the conversion of recycled reaction intermediates HCFC-123a, HCFC-133b, and HCFC-133 to HFC-143 using the same reactor.

[0369] The overall layout is as described above. Figure 1 The feeding system and reactor are as described in Example 1 above.

[0370] The reactor comprises a one-inch 316 SS tube filled with 50 ml of 4% Pd / C catalyst. Thermocouples are inserted into the center of the catalyst bed to read the operating temperature. The pressure control system consists of an RCV, which controls the pressure by receiving feedback from a pressure transducer placed downstream of the reactor. The reactor is operated at 250°C with an organic feed rate of 10 g / h and an H2 feed rate of 150 ml / min.

[0371] Using a sample bag filled with approximately 50 g of water to capture hydrogen chloride (HCl) and hydrogen fluoride (HF), GC-FID analysis of a sample taken from the product stream 108 after the reaction in reactor 106 was used to determine the product composition in reactor 106. Prior to GC analysis, the sample bag was heated at 60°C for one hour to ensure all organic contents were in the gas phase. The product stream 108 from reactor 106 in the first round contained the mixtures provided in the table below.

[0372] Table 30

[0373] Composition of the product stream 108 from reactor 106

[0374]

[0375] Note that the percentages provided are molar percentages of organic matter content only for the product stream 108 from reactor 106. The product stream 108 from reactor 106 also contains unreacted H2, hydrogen chloride (HCl) generated from the dehydrochlorination reaction, and hydrogen fluoride (HF) generated from the defluorination side reaction.

[0376] The product stream 108 from reactor 106 is fed into a first distillation column 110 to recover unreacted hydrogen (H2) from the top stream. The bottom stream 116 from the first distillation column 110 is fed into a second distillation column 118 to remove hydrogen chloride (HCl) and ethane (HC-170) from the top stream 120. The bottom stream 122 from the second distillation column 118 is fed into a scrubber 124 to remove hydrogen fluoride (HF), and then into a third distillation column 128 to remove low-boiling molecules such as HFC-152a, HCFC-142b, HFO-1123, and HFC-143a through the top stream 130 from the third distillation column 128.

[0377] The bottom stream 132 from the third distillation column 128 is fed to the fourth distillation column 134. The top stream 136 from the fourth distillation column 134 contains HFC-143 with a purity greater than 91% and impurities less than 9%, such as HCFC-133b and HCFC-133. The bottom stream 138 from the fourth distillation column 134 contains the following mixtures provided in the table below.

[0378] Table 31

[0379] Composition of bottom feed flow

[0380]

[0381] The bottom stream 138 from the fourth distillation column 134 is returned to the reactor 106 via a recirculation stream to recycle the intermediates HCFC-133b, HCFC-133 and HCFC-123a.

[0382] Example 5

[0383] Two-reactor method for producing HFC-143

[0384] This embodiment illustrates the conversion of CFC-113 to HFC-143 in a first reactor, and the conversion of recycled reaction intermediates HCFC-123a, HCFC-133b and HCFC-133 to HFC-143 in a second reactor.

[0385] The overall layout is as described above. Figure 2 The feeding system and reactor are as described in Example 1 above.

[0386] The reactor comprises a one-inch 316 SS tube filled with 50 ml of 4% Pd / C catalyst. Thermocouples are inserted into the center of the catalyst bed to read the operating temperature. The pressure control system consists of an RCV, which controls the pressure by receiving feedback from a pressure transducer placed downstream of the reactor. The reactor is operated at 250°C with an organic feed rate of 10 g / h and an H2 feed rate of 150 ml / min.

[0387] Using a sample bag filled with approximately 50 g of water to capture hydrogen chloride (HCl) and hydrogen fluoride (HF), GC-FID analysis of the sample taken after the hydrogenation reaction was used to determine the product composition in product stream 208 from the first reactor 206. Prior to GC analysis, the sample bag was heated at 60°C for one hour to ensure all organic contents were in the gas phase. Product stream 208 from the first reactor 206 contains the mixtures provided in the table below.

[0388] Table 32

[0389] Composition of the product stream 208 from the first reactor 206

[0390]

[0391] Note that the percentages provided are molar percentages of the organic content of the product stream only. The product stream also contains unreacted H2, hydrogen chloride (HCl) generated from the dehydrochlorination reaction, and hydrogen fluoride (HF) generated from the defluorination side reaction.

[0392] The product stream 208 from the first reactor 206 is fed into the first distillation column 210 to recover unreacted H2. The bottom stream 216 from the first distillation column 210 is fed into the second distillation column 218 to remove hydrogen chloride (HCl) and ethane (HC-170). The bottom stream 222 from the second distillation column 218 is fed into a scrubber 224 to remove hydrogen fluoride (HF), and then into the third distillation column 228 to remove low-boiling molecules, such as 1,1-difluoroethane (HFC-152a), HCFC-142b isomers (1-chloro-1,1-difluoroethane), 1,1,2-trifluoroethylene (HFO-1123), and 1,1,1-trifluoroethane (HFC-143a), through the top stream 230 from the third distillation column 228. The bottom stream 232 from the third distillation column 228 is fed into the fourth distillation column 234. The top stream 236 from the fourth distillation column 234 contains HFC-143 with a purity greater than 91% and impurities less than 9%, such as HCFC-133b and HCFC-133. The bottom stream 238 from the fourth distillation column 234 (in the first round before the recycle intermediate) contains the following mixtures provided in the table below.

[0393] Table 33

[0394] Composition of the bottom stream 238 from the fourth distillation column 234

[0395]

[0396] The bottom stream 238 from the fourth distillation column 234 is also fed to the second reactor 240 of the dual-reactor process. The second reactor 240 consists of a one-inch 316 SS tube filled with 50 ml of 4% Pd / C catalyst. Thermocouples are inserted into the center of the catalyst bed to read the operating temperature. The pressure control system consists of an RCV, which controls the pressure by receiving feedback from a pressure transducer placed after the second reactor 240. The second reactor 240 is operated at 45 psig, 280 °C, with an organic feed rate of 10 g / h and an H2 feed rate of 150 ml / min. Using sample bags filled with approximately 50 g of water to capture hydrogen chloride (HCl) and hydrogen fluoride (HF), GC-FID analysis of samples obtained after the second reactor 240 is used to determine the product composition in the second product stream 242 from the second reactor 240. Prior to GC analysis, the sample bags are heated at 60 °C for one hour to ensure all organic contents are in the gas phase. Under these conditions, the conversion rates of HCFC-133b, HCFC-133, and HCFC-123a were 52%, 72%, and 100%, respectively, based on the total molar number of organic components in the composition. The chloroethane (HCC-160) and HCFC-142 isomers (e.g., 1-chloro-1,2-difluoroethane (HCFC-142a), 1-chloro-2,2-difluoroethane (HCFC-142), and / or 1-chloro-1,1-difluoroethane (HCFC-142b)) were also converted to ethane (HC-170) and 1,2-difluoroethane (HFC-152) in the reactor (conversion rate of approximately 90% based on the total molar number of organic components in the composition).

[0397] The product stream 242 from the second reactor 240 (in the first round of the recycling intermediate) contains the following mixtures provided in the table below.

[0398] Table 34

[0399] Composition of the product stream from the second reactor

[0400]

[0401] The product stream 242 from the second reactor 240 is mixed with the product stream 208 from the first reactor 206 and fed to the same distillation column and scrubber as described above.

[0402] Example 6

[0403] Single-reactor method using Pt / C as catalyst

[0404] Example 6 illustrates the conversion using a 0.5% Pt / C catalyst and the same overall layout and reaction conditions as in Example 1, with a feed containing 83% CFC-113 and 17% HCFC-123a. 50 ml of pure catalyst was charged into the reactor. The organic matter flow rate was 10 g / h, and the hydrogen flow rate was 300 ml / min. The reaction was carried out at 45 psig. GC-FID analysis results of the reactor effluent as a function of catalyst bed temperature are shown in the table below.

[0405] Tables 35 and 36 show the GC-FID area percentage of the product stream of the Pt / C catalyst at the specified temperatures.

[0406] Table 35

[0407] Using a 0.5% Pt / C catalyst, for a feed containing 83% CFC-113 and 17% HCFC-123a, in the reactor Desired intermediates in subsequent product compositions

[0408]

[0409] Table 36

[0410] Using a 0.5% Pt / C catalyst, for a feed containing 83% CFC-113 and 17% HCFC-123a, in the reactor Undesirable byproducts in subsequent product compositions

[0411]

[0412] Example 7

[0413] Single-reactor method using Rh / Al2O3 as catalyst

[0414] Example 7 illustrates the conversion using a 0.5% Rh / Al₂O₃ catalyst and the same overall layout and reaction conditions as in Example 1, with a feed containing 83% CFC-113 and 17% HCFC-123a. 10 ml of catalyst was diluted with a 40 ml SS sieve. The organic matter flow rate was 10 g / h, and the hydrogen flow rate was 300 ml / min. The reaction was carried out at 45 psig. GC-FID analysis results of the reactor effluent as a function of catalyst bed temperature are shown in the table below.

[0415] Tables 37 and 38 show the GC-FID area percentage of the product stream of the Rh / Al2O3 catalyst at the specified temperatures.

[0416] Table 37

[0417] Using a 0.5% Rh / Al2O3 catalyst, for a feed containing 83% CFC-113 and 17% HCFC-123a, in the reaction... Desired intermediates in the product composition following the reactor

[0418]

[0419] Table 38

[0420] Using a 0.5% Rh / Al2O3 catalyst, for a feed containing 83% CFC-113 and 17% HCFC-123a, in the reaction... Undesirable byproducts in the product composition following the reactor

[0421]

[0422] Example 8

[0423] A dual-reactor method for producing HFC-143 with improved efficiency of tower 134.

[0424] This embodiment illustrates the conversion of CFC-113 to HFC-143 in a first reactor, and the recycling of reaction intermediates HCFC-123a, HCFC-133b, and the conversion of HCFC-133 to HFC-143 in a second reactor. The overall layout and reaction system are the same as in Example 5, but the efficiency of the distillation step performed in column 234 is improved, so that feed stream 236 contains HFC-143 with a purity greater than 95% and impurities less than 5%, such as HCFC-133b, HCFC-133, and HCC-160. Feed stream 238 (in the first round before the recycled intermediates) contains the following mixtures provided in Table 39 below.

[0425] Table 39

[0426] Composition of the bottom stream 238 from the fourth distillation column 234

[0427]

[0428] The bottom stream 238 from the fourth distillation column 234 is also fed to the second reactor 240 of the dual-reactor method. The second reactor 240 comprises a one-inch 316 SS tube packed with 50 ml of 4% Pd / C catalyst. A thermocouple is inserted in the middle of the catalyst bed to read the operating temperature. The pressure control system consists of an RCV, which controls the pressure by receiving feedback from a pressure transducer placed downstream of the second reactor 240. The second reactor 240 operates at 45 psig, 280°C, with an organic feed rate of 10 g / h and an H2 feed rate of 150 ml / min.

[0429] Using a sample bag filled with approximately 50 g of water to capture hydrogen chloride (HCl) and hydrogen fluoride (HF), GC-FID analysis of the sample obtained after the second reactor 240 was used to determine the product composition in the second product stream 242 from the second reactor 240. Prior to GC analysis, the sample bag was heated at 60°C for one hour to ensure all organic contents were in the gas phase.

[0430] Under these conditions, the conversion rates of HCFC-133b, HCFC-133, and HCFC-123a were 52%, 72%, and 100%, respectively, based on the total molar number of organic components in the composition. Chloroethane (HCC-160) and HCFC-142 isomers (e.g., 1-chloro-1,2-difluoroethane (HCFC-142a), 1-chloro-2,2-difluoroethane (HCFC-142), and / or 1-chloro-1,1-difluoroethane (HCFC-142b)) were also converted to ethane (HC-170) and difluoroethane (HFC-152 isomers) in the reactor (conversion rate of approximately 90% based on the total molar number of organic components in the composition).

[0431] The product stream 242 from the second reactor 240 (in the first round of the recycling intermediate) contains the following mixtures provided in Table 40 below.

[0432] Table 40

[0433] Composition of the product stream from the second reactor

[0434]

[0435] The product stream 242 from the second reactor 240 is mixed with the product stream 208 from the first reactor 206 and fed to the same distillation column and scrubber as described above. As calculated from the data in Tables 39 and 40, the percentage of R-143 increases to 110 mol relative to the amount of HFC-143 in the bottom stream 238 from the fourth distillation column 234 before entering the second reactor 240.

[0436] Example 9

[0437] Formation of HFO-1132E

[0438] Using steps (ii) and (iii) as described above, the desired product (HFC-143) generated in Examples 1-5 is further reacted with a catalyst to produce HFO-1132E.

[0439] It should be understood that the foregoing description is merely illustrative of this disclosure. Various alternatives and modifications can be devised by those skilled in the art without departing from this disclosure. This disclosure is intended to cover all such alternatives, modifications, and variations that fall within the scope of the appended claims.

[0440] aspect

[0441] Aspect 1 is a method for producing 1,1,2-trifluoroethane (HFC-143), the method comprising: reacting at least one of 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 1-chloro-1,2,2-trifluoroethane (HCFC-133), and 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a) and 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) in the presence of a catalyst at a temperature of 150°C to 400°C to produce 1,1,2-trifluoroethane (HFC-143).

[0442] Aspect 2 is the method according to aspect 1, wherein the catalyst is palladium metal supported on a carbon support.

[0443] Aspect 3 is the method according to aspect 2, wherein the catalyst comprises about 1% to about 5% by weight of palladium metal supported on a carbon support.

[0444] Aspect 4 is the method according to aspect 2, wherein the catalyst comprises about 4% by weight of palladium metal supported on a carbon support.

[0445] Aspect 5 is the method according to any one of aspects 1 to 4, wherein the reaction step is carried out at a temperature of 200°C to 400°C or 225°C to 350°C.

[0446] Aspect 6 is the method according to any one of aspects 1 to 5, wherein the reaction step is carried out at a temperature of 250°C to 325°C.

[0447] Aspect 7 is the method according to any one of Aspects 1 to 6, wherein the reaction step produces a composition comprising: 45 mol% to 99.97 mol% of 1,1,2-trifluoroethane (HFC-143) based on the total combined moles of HFC-143, HCFC-133b, HCFC-133 and HCFC-123a in the product composition; 0.01 mol% to 40 mol% of 1-chloro-1,1,2-trifluoroethane (HCFC-133b); 0.01 mol% to 5 mol% of 1-chloro-1,2,2-trifluoroethane (HCFC-133); and 0.01 mol% to 10 mol% of 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a).

[0448] Aspect 8 is the method according to any one of Aspects 1 to 6, wherein the reaction step produces a composition comprising, based on the total molar number of the organic components of the composition, at least 80 mol% of the total amount of 1,1,2-trifluoroethane (HFC-143), 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 1-chloro-1,2,2-trifluoroethane (HCFC-133) and 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a).

[0449] Aspect 9 is the method according to any one of Aspects 1 to 8, the method further comprising: after the reaction step, recycling at least one of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113), 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 1-chloro-1,2,2-trifluoroethane (HCFC-133), and 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a) back to an additional step of the reaction step in the form of a recycling stream.

[0450] Aspect 10 is the method according to aspect 9, wherein, based on the total combined molar number of HFC-143, HCFC-133b, HCFC-133 and HCFC-123a in the recycled stream, the recycled stream comprises: 0.01 mol% to 20 mol% of 1,1,2-trifluoroethane (HFC-143); 40 mol% to 99.93 mol% of 1-chloro-1,1,2-trifluoroethane (HCFC-133b); 0.01 mol% to 20 mol% of 1-chloro-1,2,2-trifluoroethane (HCFC-133); and 0.01 mol% to 20 mol% of 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a).

[0451] Aspect 11 is the method according to any one of Aspects 1 to 10, the method further comprising reacting 1,1,2-trifluoroethane (HFC-143) with a catalyst to produce trans-1,2-difluoroethylene (HFO-1132E).

[0452] Aspect 12 is a method for producing 1,1,2-trifluoroethane (HFC-143), the method comprising reacting 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) with hydrogen in the presence of a catalyst to produce a first product composition comprising 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 1-chloro-1,2,2-trifluoroethane (HCFC-133), and 1,2-dichloro-1,1,2-trifluoroethane (HCFC-143b). The first product composition comprises at least one of 23a) and 1,1,2-trifluoroethane (HFC-143); and at least one of 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 1-chloro-1,2,2-trifluoroethane (HCFC-133), and 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a) from the first product composition is reacted with hydrogen in the presence of a catalyst to produce a second product composition comprising 1,1,2-trifluoroethane (HFC-143). The first reaction step can be carried out at a temperature of 150°C to 400°C or 200°C to 400°C. The second reaction step can be carried out at a temperature of 200°C to 450°C or 225°C to 400°C.

[0453] Aspect 13 is the method according to aspect 12, wherein the method further comprises, between the first reaction step and the second reaction step, the following additional steps: removing hydrogen and acid to produce a substantially acid-free feed stream; and distilling the substantially acid-free feed stream to produce a top composition comprising 1,1,2-trifluoroethane (HFC-143) and a bottom composition comprising 1-chloro-1,1,2-trifluoroethane (CFC-133b).

[0454] Aspect 14 is the method according to aspect 12 or aspect 13, wherein the catalyst is palladium metal supported on a carbon support.

[0455] Aspect 15 is the method according to aspect 14, wherein the catalyst comprises about 4% by weight of palladium metal supported on a carbon support.

[0456] Aspect 16 is the method according to any one of aspects 12 to 15, wherein the second reaction step is carried out at a temperature of 250°C to 450°C.

[0457] Aspect 17 is the method according to any one of aspects 12 to 15, wherein the second reaction step is carried out at a temperature of 275°C to 400°C.

[0458] Aspect 18 is the method according to any one of aspects 12 to 17, wherein the second reaction step produces a composition comprising: 50 mol% to 99.97 mol% of 1,1,2-trifluoroethane (HFC-143) based on the total combined moles of HFC-143, HCFC-133b, HCFC-133 and HCFC-123a in the composition; 0.01 mol% to 40 mol% of 1-chloro-1,1,2-trifluoroethane (HCFC-133b); 0.01 mol% to 10 mol% of 1-chloro-1,2,2-trifluoroethane (HCFC-133); and 0.01 mol% to 10 mol% of 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a).

[0459] Aspect 19 is the method according to any one of aspects 12 to 17, wherein the second reaction step produces a composition comprising, based on the total molar number of the organic components of the composition, a total amount of 1,1,2-trifluoroethane (HFC-143), 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 1-chloro-1,2,2-trifluoroethane (HCFC-133) and 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a) of 80 mol% to 99.9 mol%.

[0460] Aspect 20 is the method according to any one of aspects 12 to 19, the method further comprising: after the second reaction step, recycling at least one of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113), 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 1-chloro-1,2,2-trifluoroethane (HCFC-133), and 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a) back to an additional step of the reaction step in the form of a recycling stream.

[0461] Aspect 21 is the method according to aspect 20, wherein, based on the total combined molar number of HFC-143, HCFC-133b, HCFC-133 and HCFC-123a in the recycled stream, the recycled stream comprises: 50 mol% to 99.97 mol% of 1,1,2-trifluoroethane (HFC-143); 0.01 mol% to 40 mol% of 1-chloro-1,1,2-trifluoroethane (HCFC-133b); 0.01 mol% to 5 mol% of 1-chloro-1,2,2-trifluoroethane (HCFC-133); and 0.01 mol% to 5 mol% of 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a).

[0462] Aspect 22 is the method according to any one of aspects 12 to 21, the method further comprising reacting at least one of the 1,1,2-trifluoroethane (HFC-143) of the first product composition and the 1,1,2-trifluoroethane (HFC-143) of the second product composition with a catalyst to produce trans-1,2-difluoroethylene (HFO-1132E).

[0463] Aspect 23 is the method according to any one of aspects 1 to 8, wherein the catalyst comprises about 0.5% by weight to about 10% by weight of palladium metal supported on a carbon support; wherein the reaction step is carried out at a temperature of about 200°C to about 350°C.

[0464] Aspect 24 is the method according to any one of aspects 1 to 8, wherein the catalyst comprises about 0.5% by weight to about 10% by weight of palladium metal supported on a carbon support; wherein the reaction step is carried out at a temperature of about 230°C to about 290°C.

[0465] Aspect 25 is the method according to any one of aspects 1 to 8, wherein the catalyst comprises about 0.5% by weight to about 10% by weight of palladium metal supported on a carbon support; wherein the reaction step is carried out at a temperature of about 250°C to about 280°C.

[0466] Aspect 26 is the method according to any one of aspects 1 to 8, wherein the catalyst comprises about 0.5% by weight to about 10% by weight of palladium metal supported on a carbon support; wherein the reaction step is carried out at a temperature of about 250°C to about 350°C.

[0467] Aspect 27 is the method according to any one of aspects 1 to 8, wherein the catalyst comprises about 1% to about 5% by weight of palladium metal supported on a carbon support; wherein the reaction step is carried out at a temperature of about 200°C to about 350°C.

[0468] Aspect 28 is the method according to any one of aspects 1 to 8, wherein the catalyst comprises about 1% to about 5% by weight of palladium metal supported on a carbon support; wherein the reaction step is carried out at a temperature of about 230°C to about 290°C.

[0469] Aspect 29 is the method according to any one of aspects 1 to 8, wherein the catalyst comprises about 1% to about 5% by weight of palladium metal supported on a carbon support; wherein the reaction step is carried out at a temperature of about 250°C to about 280°C.

[0470] Aspect 30 is the method according to any one of aspects 1 to 8, wherein the catalyst comprises about 1% to about 5% by weight of palladium metal supported on a carbon support; wherein the reaction step is carried out at a temperature of about 250°C to about 350°C.

[0471] Aspect 31 is the method according to any one of aspects 1 to 8, wherein the catalyst comprises about 0.1 wt% to about 10 wt% of palladium metal supported on an α-alumina support; wherein the reaction step is carried out at a temperature of about 200°C to about 350°C.

[0472] Aspect 32 is the method according to any one of aspects 1 to 8, wherein the catalyst comprises about 0.1 wt% to about 10 wt% of palladium metal supported on an α-alumina support; wherein the reaction step is carried out at a temperature of about 230°C to about 290°C.

[0473] Aspect 33 is the method according to any one of aspects 1 to 8, wherein the catalyst comprises about 0.1 wt% to about 10 wt% of palladium metal supported on an α-alumina support; wherein the reaction step is carried out at a temperature of about 250°C to about 280°C.

[0474] Aspect 34 is the method according to any one of aspects 1 to 8, wherein the catalyst comprises about 0.1 wt% to about 10 wt% of palladium metal supported on an α-alumina support; wherein the reaction step is carried out at a temperature of about 250°C to about 350°C.

[0475] Aspect 35 is the method according to any one of aspects 1 to 8, wherein the catalyst comprises about 0.2% by weight to about 5% by weight of palladium metal supported on an α-alumina support; wherein the reaction step is carried out at a temperature of about 200°C to about 350°C.

[0476] Aspect 36 is the method according to any one of aspects 1 to 8, wherein the catalyst comprises about 0.2% by weight to about 5% by weight of palladium metal supported on an α-alumina support; wherein the reaction step is carried out at a temperature of about 230°C to about 290°C.

[0477] Aspect 37 is the method according to any one of aspects 1 to 8, wherein the catalyst comprises about 0.2% by weight to about 5% by weight of palladium metal supported on an α-alumina support; wherein the reaction step is carried out at a temperature of about 250°C to about 280°C.

[0478] Aspect 38 is the method according to any one of aspects 1 to 8, wherein the catalyst comprises about 0.2% by weight to about 5% by weight of palladium metal supported on an α-alumina support; wherein the reaction step is carried out at a temperature of about 250°C to about 350°C.

[0479] Aspect 39 is the method according to any one of aspects 12 to 19, wherein for the first reaction step, the catalyst comprises about 0.5% by weight to about 10% by weight of palladium metal supported on a carbon support; wherein the first reaction step is carried out at a temperature of about 200°C to about 400°C.

[0480] Aspect 40 is the method according to any one of aspects 12 to 19, wherein for the first reaction step, the catalyst comprises about 0.5% by weight to about 10% by weight of palladium metal supported on a carbon support; wherein the first reaction step is carried out at a temperature of about 220°C to about 400°C.

[0481] Aspect 41 is the method according to any one of aspects 12 to 19, wherein for the first reaction step, the catalyst comprises about 0.5% by weight to about 10% by weight of palladium metal supported on a carbon support; wherein the first reaction step is carried out at a temperature of about 240°C to about 350°C.

[0482] Aspect 42 is the method according to any one of aspects 12 to 19, wherein for the first reaction step, the catalyst comprises about 0.5% by weight to about 10% by weight of palladium metal supported on a carbon support; wherein the first reaction step is carried out at a temperature of about 250°C to about 300°C.

[0483] Aspect 43 is the method according to any one of aspects 12 to 19, wherein for the first reaction step, the catalyst comprises about 1% to about 5% by weight of palladium metal supported on a carbon support; wherein the first reaction step is carried out at a temperature of about 200°C to about 400°C.

[0484] Aspect 44 is the method according to any one of aspects 12 to 19, wherein for the first reaction step, the catalyst comprises about 1% to about 5% by weight of palladium metal supported on a carbon support; wherein the first reaction step is carried out at a temperature of about 220°C to about 400°C.

[0485] Aspect 45 is the method according to any one of aspects 12 to 19, wherein for the first reaction step, the catalyst comprises about 1% to about 5% by weight of palladium metal supported on a carbon support; wherein the first reaction step is carried out at a temperature of about 240°C to about 350°C.

[0486] Aspect 46 is the method according to any one of aspects 12 to 19, wherein for the first reaction step, the catalyst comprises about 1% to about 5% by weight of palladium metal supported on a carbon support; wherein the first reaction step is carried out at a temperature of about 250°C to about 300°C.

[0487] Aspect 47 is the method according to any one of aspects 12 to 19, wherein for the first reaction step, the catalyst comprises about 2% to about 4% by weight of palladium metal supported on a carbon support; wherein the first reaction step is carried out at a temperature of about 200°C to about 400°C.

[0488] Aspect 48 is the method according to any one of aspects 12 to 19, wherein for the first reaction step, the catalyst comprises about 2% to about 4% by weight of palladium metal supported on a carbon support; wherein the first reaction step is carried out at a temperature of about 220°C to about 400°C.

[0489] Aspect 49 is the method according to any one of aspects 12 to 19, wherein for the first reaction step, the catalyst comprises about 2% to about 4% by weight of palladium metal supported on a carbon support; wherein the first reaction step is carried out at a temperature of about 240°C to about 350°C.

[0490] Aspect 50 is the method according to any one of aspects 12 to 19, wherein for the first reaction step, the catalyst comprises about 2% to about 4% by weight of palladium metal supported on a carbon support; wherein the first reaction step is carried out at a temperature of about 250°C to about 300°C.

[0491] Aspect 51 is the method according to any one of aspects 12 to 19, wherein for the first reaction step, the catalyst comprises about 0.1 wt% to about 10 wt% of palladium metal supported on an α-alumina support; wherein the first reaction step is carried out at a temperature of about 150°C to about 350°C.

[0492] Aspect 52 is the method according to any one of aspects 12 to 19, wherein for the first reaction step, the catalyst comprises about 0.1 wt% to about 10 wt% of palladium metal supported on an α-alumina support; wherein the first reaction step is carried out at a temperature of about 150°C to about 250°C.

[0493] Aspect 53 is the method according to any one of aspects 12 to 19, wherein for the first reaction step, the catalyst comprises about 0.2% by weight to about 5% by weight of palladium metal supported on an α-alumina support; wherein the first reaction step is carried out at a temperature of about 150°C to about 350°C.

[0494] Aspect 54 is the method according to any one of aspects 12 to 19, wherein for the first reaction step, the catalyst comprises about 0.2% by weight to about 5% by weight of palladium metal supported on an α-alumina support; wherein the first reaction step is carried out at a temperature of about 150°C to about 250°C.

[0495] Aspect 55 is the method according to any one of aspects 12 to 19, wherein for the second reaction step, the catalyst comprises about 0.1 wt% to about 10 wt% of palladium metal supported on a carbon support; wherein the second reaction step is carried out at a temperature of about 200°C to about 450°C.

[0496] Aspect 56 is the method according to any one of aspects 12 to 19, wherein for the second reaction step, the catalyst comprises about 0.1 wt% to about 10 wt% of palladium metal supported on a carbon support; wherein the second reaction step is carried out at a temperature of about 220°C to about 400°C.

[0497] Aspect 57 is the method according to any one of aspects 12 to 19, wherein for the second reaction step, the catalyst comprises about 0.1% by weight to about 10% by weight of palladium metal supported on a carbon support; wherein the second reaction step is carried out at a temperature of about 250°C to about 350°C.

[0498] Aspect 58 is the method according to any one of aspects 12 to 19, wherein for the second reaction step, the catalyst comprises about 0.1% by weight to about 10% by weight of palladium metal supported on a carbon support; wherein the second reaction step is carried out at a temperature of about 275°C to about 350°C.

[0499] Aspect 59 is the method according to any one of aspects 12 to 19, wherein for the second reaction step, the catalyst comprises about 0.5% by weight to about 5% by weight of palladium metal supported on a carbon support; wherein the second reaction step is carried out at a temperature of about 200°C to about 450°C.

[0500] Aspect 60 is the method according to any one of aspects 12 to 19, wherein for the second reaction step, the catalyst comprises about 0.5% by weight to about 5% by weight of palladium metal supported on a carbon support; wherein the second reaction step is carried out at a temperature of about 220°C to about 400°C.

[0501] Aspect 61 is the method according to any one of aspects 12 to 19, wherein for the second reaction step, the catalyst comprises about 0.5% by weight to about 5% by weight of palladium metal supported on a carbon support; wherein the second reaction step is carried out at a temperature of about 250°C to about 350°C.

[0502] Aspect 62 is the method according to any one of aspects 12 to 19, wherein for the second reaction step, the catalyst comprises about 0.5% by weight to about 5% by weight of palladium metal supported on a carbon support; wherein the second reaction step is carried out at a temperature of about 275°C to about 350°C.

[0503] Aspect 63 is the method according to any one of aspects 12 to 19, wherein for the second reaction step, the catalyst comprises about 1% to about 4% by weight of palladium metal supported on a carbon support; wherein the second reaction step is carried out at a temperature of about 200°C to about 450°C.

[0504] Aspect 64 is the method according to any one of aspects 12 to 19, wherein for the second reaction step, the catalyst comprises about 1% to about 4% by weight of palladium metal supported on a carbon support; wherein the second reaction step is carried out at a temperature of about 220°C to about 400°C.

[0505] Aspect 65 is the method according to any one of aspects 12 to 19, wherein for the second reaction step, the catalyst comprises about 1% to about 4% by weight of palladium metal supported on a carbon support; wherein the second reaction step is carried out at a temperature of about 250°C to about 350°C.

[0506] Aspect 66 is the method according to any one of aspects 12 to 19, wherein for the second reaction step, the catalyst comprises about 1% to about 4% by weight of palladium metal supported on a carbon support; wherein the second reaction step is carried out at a temperature of about 275°C to about 350°C.

[0507] Aspect 67 is the method according to any one of aspects 12 to 19, wherein for the second reaction step, the catalyst comprises about 0.1 wt% to about 10 wt% of palladium metal supported on an α-alumina support; wherein the second reaction step is carried out at a temperature of about 150°C to about 350°C.

[0508] Aspect 68 is the method according to any one of aspects 12 to 19, wherein for the second reaction step, the catalyst comprises about 0.1 wt% to about 10 wt% of palladium metal supported on an α-alumina support; wherein the second reaction step is carried out at a temperature of about 150°C to about 250°C.

[0509] Aspect 69 is the method according to any one of aspects 12 to 19, wherein for the second reaction step, the catalyst comprises about 0.2% by weight to about 5% by weight of palladium metal supported on an α-alumina support; wherein the second reaction step is carried out at a temperature of about 150°C to about 350°C.

[0510] Aspect 71 is the method according to any one of aspects 12 to 19, wherein for the second reaction step, the catalyst comprises about 0.2% by weight to about 5% by weight of palladium metal supported on an α-alumina support; wherein the second reaction step is carried out at a temperature of about 150°C to about 250°C.

[0511] Aspect 72 is a composition comprising: 45 mol% to 99.97 mol% of 1,1,2-trifluoroethane (HFC-143) based on the total combined moles of HFC-143, HCFC-133b, HCFC-133 and HCFC-123a in the composition; 0.01 mol% to 40 mol% of 1-chloro-1,1,2-trifluoroethane (HCFC-133b); 0.01 mol% to 5 mol% of 1-chloro-1,2,2-trifluoroethane (HCFC-133); and 0.01 mol% to 10 mol% of 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a).

[0512] Aspect 73 is a composition comprising: 0.01 mol% to 20 mol% of 1,1,2-trifluoroethane (HFC-143) based on the total combined moles of HFC-143, HCFC-133b, HCFC-133 and HCFC-123a in the composition; 40 mol% to 99.97 mol% of 1-chloro-1,1,2-trifluoroethane (HCFC-133b); 0.01 mol% to 20 mol% of 1-chloro-1,2,2-trifluoroethane (HCFC-133); and 0.01 mol% to 20 mol% of 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a).

[0513] Aspect 74 is a composition comprising: 0.01 mol% to 50 mol% of 1,1,2-trifluoroethane (HFC-143) based on the total combined moles of HFC-143, HCFC-133b, HCFC-133 and HCFC-123a in the composition; 20 mol% to 99.97 mol% of 1-chloro-1,1,2-trifluoroethane (HCFC-133b); 0.01 mol% to 10 mol% of 1-chloro-1,2,2-trifluoroethane (HCFC-133); and 0.01 mol% to 20 mol% of 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a).

[0514] Aspect 75 is a composition comprising: 40 mol% to 99.97 mol% of 1,1,2-trifluoroethane (HFC-143) based on the total combined moles of HFC-143, HCFC-133b, HCFC-133 and HCFC-123a in the composition; 0.01 mol% to 40 mol% of 1-chloro-1,1,2-trifluoroethane (HCFC-133b); 0.01 mol% to 10 mol% of 1-chloro-1,2,2-trifluoroethane (HCFC-133); and 0.01 mol% to 10 mol% of 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a).

[0515] Aspect 76 is a composition comprising: 50 mol% to 99.97 mol% of 1,1,2-trifluoroethane (HFC-143) based on the total combined moles of HFC-143, HCFC-133b, HCFC-133 and HCFC-123a in the composition; 0.01 mol% to 40 mol% of 1-chloro-1,1,2-trifluoroethane (HCFC-133b); 0.01 mol% to 5 mol% of 1-chloro-1,2,2-trifluoroethane (HCFC-133); and 0.01 mol% to 5 mol% of 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a).

[0516] Aspect 77 is the method according to aspect 12, wherein the first reaction step produces a composition comprising: 45 mol% to 99.97 mol% of 1,1,2-trifluoroethane (HFC-143) based on the total combined moles of HFC-143, HCFC-133b, HCFC-133 and HCFC-123a in the composition; 0.01 mol% to 40 mol% of 1-chloro-1,1,2-trifluoroethane (HCFC-133b); 0.01 mol% to 5 mol% of 1-chloro-1,2,2-trifluoroethane (HCFC-133); and 0.01 mol% to 10 mol% of 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a).

[0517] Aspect 78 is the method according to aspect 13, wherein the distillation step produces a first distillate composition; wherein the second reaction step produces a second composition; wherein the amount of 1,1,2-trifluoroethane (HFC-143) in the second composition is increased by 35 mol% to 130 mol relative to the amount of 1,1,2-trifluoroethane (HFC-143) in the first distillate composition.

[0518] Aspect 79 is the method according to aspect 13, wherein the distillation step produces a first distillate composition; wherein the second reaction step produces a second composition; wherein the amount of 1,1,2-trifluoroethane (HFC-143) in the second composition is increased by 40 mol% to 130 mol relative to the amount of 1,1,2-trifluoroethane (HFC-143) in the first distillate composition.

[0519] Aspect 80 is the method according to aspect 13, wherein the distillation step produces a distillate composition comprising: 0.01 mol% to 50 mol% of 1,1,2-trifluoroethane (HFC-143) based on the total combined moles of HFC-143, HCFC-133b, HCFC-133 and HCFC-123a in the distillate composition; 20 mol% to 99.97 mol% of 1-chloro-1,1,2-trifluoroethane (HCFC-133b); 0.01 mol% to 10 mol% of 1-chloro-1,2,2-trifluoroethane (HCFC-133); and 0.01 mol% to 20 mol% of 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a).

[0520] Aspect 81 is the method according to any one of aspects 1 to 8, wherein the catalyst comprises about 0.5% by weight to about 10% by weight of rhodium metal supported on a carbon support; wherein the reaction step is carried out at a temperature of about 200°C to about 350°C.

[0521] Aspect 82 is the method according to any one of aspects 1 to 8, wherein the catalyst comprises about 0.5% by weight to about 10% by weight of rhodium metal supported on a carbon support; wherein the reaction step is carried out at a temperature of about 230°C to about 290°C.

[0522] Aspect 83 is the method according to any one of aspects 1 to 8, wherein the catalyst comprises about 0.5% by weight to about 10% by weight of rhodium metal supported on a carbon support; wherein the reaction step is carried out at a temperature of about 250°C to about 280°C.

[0523] Aspect 84 is the method according to any one of aspects 1 to 8, wherein the catalyst comprises about 0.5% by weight to about 10% by weight of rhodium metal supported on a carbon support; wherein the reaction step is carried out at a temperature of about 250°C to about 350°C.

[0524] Aspect 85 is the method according to any one of aspects 1 to 8, wherein the catalyst comprises about 1% to about 5% by weight of rhodium metal supported on a carbon support; wherein the reaction step is carried out at a temperature of about 200°C to about 350°C.

[0525] Aspect 86 is the method according to any one of aspects 1 to 8, wherein the catalyst comprises about 1% to about 5% by weight of rhodium metal supported on a carbon support; wherein the reaction step is carried out at a temperature of about 230°C to about 290°C.

[0526] Aspect 87 is the method according to any one of aspects 1 to 8, wherein the catalyst comprises about 1% to about 5% by weight of rhodium metal supported on a carbon support; wherein the reaction step is carried out at a temperature of about 250°C to about 280°C.

[0527] Aspect 88 is the method according to any one of aspects 1 to 8, wherein the catalyst comprises about 1% to about 5% by weight of rhodium metal supported on a carbon support; wherein the reaction step is carried out at a temperature of about 250°C to about 350°C.

[0528] Aspect 89 is the method according to any one of aspects 1 to 8, wherein the catalyst comprises about 0.1 wt% to about 10 wt% of rhodium metal supported on an α-alumina support; wherein the reaction step is carried out at a temperature of about 200°C to about 350°C.

[0529] Aspect 90 is the method according to any one of aspects 1 to 8, wherein the catalyst comprises about 0.1 wt% to about 10 wt% of rhodium metal supported on an α-alumina support; wherein the reaction step is carried out at a temperature of about 230°C to about 290°C.

[0530] Aspect 91 is the method according to any one of aspects 1 to 8, wherein the catalyst comprises about 0.1% by weight to about 10% by weight of rhodium metal supported on an α-alumina support; wherein the reaction step is carried out at a temperature of about 250°C to about 280°C.

[0531] Aspect 92 is the method according to any one of aspects 1 to 8, wherein the catalyst comprises about 0.1% by weight to about 10% by weight of rhodium metal supported on an α-alumina support; wherein the reaction step is carried out at a temperature of about 250°C to about 350°C.

[0532] Aspect 93 is the method according to any one of aspects 1 to 8, wherein the catalyst comprises about 0.2% by weight to about 5% by weight of rhodium metal supported on an α-alumina support; wherein the reaction step is carried out at a temperature of about 200°C to about 350°C.

[0533] Aspect 94 is the method according to any one of aspects 1 to 8, wherein the catalyst comprises about 0.2% by weight to about 5% by weight of rhodium metal supported on an α-alumina support; wherein the reaction step is carried out at a temperature of about 230°C to about 290°C.

[0534] Aspect 95 is the method according to any one of aspects 1 to 8, wherein the catalyst comprises about 0.2% by weight to about 5% by weight of rhodium metal supported on an α-alumina support; wherein the reaction step is carried out at a temperature of about 250°C to about 280°C.

[0535] Aspect 96 is the method according to any one of aspects 1 to 8, wherein the catalyst comprises about 0.2% by weight to about 5% by weight of rhodium metal supported on an α-alumina support; wherein the reaction step is carried out at a temperature of about 250°C to about 350°C.

[0536] Aspect 97 is the method according to any one of aspects 12 to 19, wherein for the first reaction step, the catalyst comprises about 0.5% by weight to about 10% by weight of rhodium metal supported on a carbon support; wherein the first reaction step is carried out at a temperature of about 200°C to about 400°C.

[0537] Aspect 98 is the method according to any one of aspects 12 to 19, wherein for the first reaction step, the catalyst comprises about 1% to about 5% by weight of rhodium metal supported on a carbon support; wherein the first reaction step is carried out at a temperature of about 250°C to about 350°C.

[0538] Aspect 99 is the method according to any one of aspects 12 to 19, wherein for the second reaction step, the catalyst comprises about 0.1% by weight to about 10% by weight of rhodium metal supported on a carbon support; wherein the second reaction step is carried out at a temperature of about 200°C to about 450°C.

[0539] Aspect 100 is the method according to any one of aspects 12 to 19, wherein for the second reaction step, the catalyst comprises about 1% to about 4% by weight of rhodium metal supported on a carbon support; wherein the second reaction step is carried out at a temperature of about 250°C to about 350°C.

Claims

1. A method for producing 1,1,2-trifluoroethane (HFC-143), the method comprising: At least one of 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 1-chloro-1,2,2-trifluoroethane (HCFC-133), and 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a), as well as 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113), are reacted in the presence of a catalyst at a temperature of 150°C to 400°C to produce 1,1,2-trifluoroethane (HFC-143).

2. The method according to claim 1, wherein the catalyst is palladium metal supported on a carbon support.

3. The method according to claim 1 or 2, wherein the reaction step produces a composition comprising: based on the total combined molar number of HFC-143, HCFC-133b, HCFC-133 and HCFC-123a in the product composition, 45 mol% to 99.97 mol% of 1,1,2-trifluoroethane (HFC-143). 0.01 mol% to 40 mol% of 1-chloro-1,1,2-trifluoroethane (HCFC-133b). 0.01 mol% to 5 mol% of 1-chloro-1,2,2-trifluoroethane (HCFC-133); and 0.01 mol% to 10 mol% of 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a).

4. The method according to any one of claims 1 to 3, wherein the reaction step produces a composition comprising, based on the total molar number of the organic components of the composition, at least 80 mol% of the total amount of 1,1,2-trifluoroethane (HFC-143), 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 1-chloro-1,2,2-trifluoroethane (HCFC-133), and 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a).

5. The method according to any one of claims 1 to 4, further comprising: Following the reaction step, at least one of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113), 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 1-chloro-1,2,2-trifluoroethane (HCFC-133), and 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a) is recycled back to an additional step of the reaction step in the form of a recycle stream; The recycle stream comprises, based on the total molar number of HFC-143, HCFC-133b, HCFC-133, and HCFC-123a in the recycle stream: 0.01 mol% to 20 mol% of 1,1,2-trifluoroethane (HFC-143); 40 mol% to 99.97 mol% of 1-chloro-1,1,2-trifluoroethane (HCFC-133b). 0.01 mol% to 20 mol% of 1-chloro-1,2,2-trifluoroethane (HCFC-133); and 0.01 mol% to 20 mol% of 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a).

6. The method according to any one of claims 1 to 5, the method further comprising reacting 1,1,2-trifluoroethane (HFC-143) with a catalyst to produce trans-1,2-difluoroethylene (HFO-1132E).

7. A method for producing 1,1,2-trifluoroethane (HFC-143), the method comprising: 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) is reacted with hydrogen in the presence of a catalyst to produce a first product composition comprising at least one of 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 1-chloro-1,2,2-trifluoroethane (HCFC-133), and 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a), and 1,1,2-trifluoroethane (HFC-143); and At least one of 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 1-chloro-1,2,2-trifluoroethane (HCFC-133), and 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a) from the first product composition is reacted with hydrogen in the presence of a catalyst to produce a second product composition comprising 1,1,2-trifluoroethane (HFC-143).

8. The method according to claim 7, The catalyst is palladium metal supported on a carbon support; The first reaction step is carried out at a temperature of 150°C to 400°C; The second reaction step is carried out at a temperature of 200°C to 450°C.

9. The method according to claim 7 or 8, wherein the first reaction step produces a composition comprising: based on the total combined molar number of HFC-143, HCFC-133b, HCFC-133 and HCFC-123a in the composition, 45 mol% to 99.97 mol% of 1,1,2-trifluoroethane (HFC-143). 0.01 mol% to 40 mol% of 1-chloro-1,1,2-trifluoroethane (HCFC-133b); 0.01 mol% to 5 mol% of 1-chloro-1,2,2-trifluoroethane (HCFC-133); and 0.01 mol% to 10 mol% of 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a).

10. The method according to claim 7, wherein the method further comprises, between the first reaction step and the second reaction step: Remove hydrogen and acid to produce a feed stream that is essentially free of acid; as well as The substantially acid-free feed stream was distilled to produce a first distillate composition containing 1,1,2-trifluoroethane (HFC-143); The amount of 1,1,2-trifluoroethane (HFC-143) in the second product composition is increased by about 35 mol% to about 130 mol% relative to the amount of 1,1,2-trifluoroethane (HFC-143) in the first distillate composition.

11. The method of claim 10, wherein the distillation step produces a distillate composition comprising: based on the total combined molar number of HFC-143, HCFC-133b, HCFC-133 and HCFC-123a in the composition, 0.01 mol% to 50 mol% of 1,1,2-trifluoroethane (HFC-143); 20 mol% to 99.97 mol% of 1-chloro-1,1,2-trifluoroethane (HCFC-133b). 0.01 mol% to 10 mol% of 1-chloro-1,2,2-trifluoroethane (HCFC-133); and 0.01 mol% to 20 mol% of 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a).

12. The method of claim 7, wherein the second reaction step produces a composition comprising: based on the total combined molar number of HFC-143, HCFC-133b, HCFC-133 and HCFC-123a in the composition, 50 mol% to 99.97 mol% of 1,1,2-trifluoroethane (HFC-143); 0.01 mol% to 40 mol% of 1-chloro-1,1,2-trifluoroethane (HCFC-133b). 0.01 mol% to 5 mol% of 1-chloro-1,2,2-trifluoroethane (HCFC-133); and 0.01 mol% to 5 mol% of 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a).

13. The method of claim 7, wherein the second reaction step produces a composition comprising, based on the total molar number of the organic components of the composition, at least 80 mol% of the total amount of 1,1,2-trifluoroethane (HFC-143), 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 1-chloro-1,2,2-trifluoroethane (HCFC-133), and 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a).

14. The method according to claim 7, further comprising: Following the second reaction step, at least one of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113), 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 1-chloro-1,2,2-trifluoroethane (HCFC-133), and 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a) is recycled back to an additional step of the reaction step as a recycle stream.

15. The method of claim 14, wherein the recycled stream comprises: based on the total combined molar number of HFC-143, HCFC-133b, HCFC-133 and HCFC-123a in the recycled stream, 50 mol% to 99.97 mol% of 1,1,2-trifluoroethane (HFC-143); 0.01 mol% to 40 mol% of 1-chloro-1,1,2-trifluoroethane (HCFC-133b). 0.01 mol% to 5 mol% of 1-chloro-1,2,2-trifluoroethane (HCFC-133); and 0.01 mol% to 5 mol% of 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a).

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